Light emitting material and organic light-emitting device

ABSTRACT

A polymer light emitting material, wherein the material has a light emitting mechanism based on transition from an excited triplet state to a ground state or transition through an excited triplet state to a ground state of an electron energy level, and the material comprises a nonionic light emitting part which constitutes a part of the polymer or is bound to the polymer. The polymer light emitting material exhibits high light emission efficiency above 5%, which is the limit of external quantum efficiency of fluorescence and can be designed so as to have a large area and hence are suitable for mass production of organic light emitting devices.

CROSS-REFERENCE TO THE RELATED APPLICATIONS

[0001] This is an application filed pursuant to 35 U.S.C. Section 111(a)with claiming the benefit of (1) U.S. Provisional application Ser. No.60/301,844 filed Jul. 2, 2001, (2) U.S. Provisional application Ser. No.60/302,372 filed Jul. 3, 2001, (3) U.S. Provisional application Ser. No.60/317,115 filed Sep. 6, 2001, (4) U.S. Provisional application Ser. No.60/330,815 filed Oct. 31, 2001, (5) U.S. Provisional application Ser.No.,60/337,157 filed Dec. 10, 2001, (6) U.S. Provisional applicationSer. No. 60/337,160 filed Dec. 10, 2001 and (7) U.S. Provisionalapplication Ser. No. 60/337,161 filed Dec. 10, 2001 under the provisionof 35 U.S.C. Section 111(b), pursuant to 35 U.S.C. Section 119(e) (1).

TECHNICAL FIELD

[0002] The present invention relates to an organic light-emitting device(OLED), especially for flat panel displays or backlights used therein,and the present invention relates to a light emitting material for OLED.

BACKGROUND ART

[0003] Since 1987 when C. W. Tang et al. of Kodak demonstrated highillumination light emission of an organic light emitting device (Appl.Phys. Lett., Vol., 51, page 913, 1987), development of materials fororganic light emitting devices and improvement of device structure havebeen rapidly made. Recently, organic light emitting devices have goneinto practical use firstly in displays for car audio sets, cellularphones and the like. Currently, to put such organic electroluminescent(EL) devices to a wider range of uses, development of materials forimproving the light emission efficiency and durability, or developmentfor applying them to full color displays are being actively made. Inparticular, on considering the use wide-spreading to the medium- orlarge-size panel or illumination, the high luminance must be moreintensified by improving the light emission efficiency.

[0004] As such light emitting materials, metal complexes such asaluminum quinolinium complexes (Alq₃), which has good light emissionefficiency so that light emission intensity is high, have beencommonly-used. For forming such low molecular weight materials into alight emitting layer of an organic light emitting device, vacuumdeposition and the like techniques have been used. This has beenconsidered to be a demerit in the production process of the organiclight emitting devices. Nature, Vol. 397, page 121 (1999) discloses thatn-electron conjugated polymers such as poly(paraphenylene-vinylene)(PPV) and derivatives thereof (MEH-PPV) can serve as a light emittingmaterial. These polymers have begun to be partially used as a backlightof a clock and the like. These polymer materials have not only a meritin production process because they can be formed into films by a castingmethod but also a merit in an increased durability as compared with lowmolecular weight light emitting materials. However, they have a demeritin that they have low light emission efficiency as compared with the lowmolecular weight light emitting materials.

[0005] In the light emitting materials as mentioned above, use is madeof light emission from an excited singlet state, that is, fluorescence.According to the description at page 58 of Monthly Display, October1998, Separate Volume “Organic EL Display”, the upper limit of theinternal quantum efficiency of light emission in an organic EL has beenconsidered to be 25% from the ratio of an excited singlet state to anexcited triplet state generated by electric excitation being 1:3.

[0006] On the contrary, by using an iridium complex emitted byphosphorescence from an excited triplet state, M. A. Baldo et al.indicated that it is possible to obtain an external quantum efficiencyof 7.5% (this corresponding to an internal quantum efficiency of 37.5%assuming that the light out-coupling efficiency is 20%), which is higherthan the external quantum efficiency of 5%, which has conventionallybeen considered to be the uppermost value (Appl. Phys. Lett., Vol.75,page 4 (1999), WO00/70655). However, materials that stably emitphosphorescence at room temperature as the iridium complex as used inthe prior art cited here are extremely rare so that freedom of selectionof materials is narrow and they must be doped to a specified hostcompound when actually used. Therefore, the conventional materials havethe disadvantage that selection of materials that satisfy thespecification of a display is extremely difficult to make.

[0007] On the other hand, M. A. Baldo et al., also indicated that arelatively good light emission efficiency can be obtained by using aniridium complex as a sensitizer, transferring energy from an excitedtriplet state of the complex to an excited singlet state of afluorescent dye, and finally emitting fluorescence from the excitedsinglet state of the fluorescent dye (Nature, Vol. 403, page 750(2000)). This method has the advantage in that from a number offluorescent dyes, one that is suitable for the purpose can be selectedand used. However, this process has the great disadvantage in that ithas low quantum efficiency of light emission in principle since itinvolves a spin-forbidden process of transferring energy from an excitedtriplet state of a sensitizer to an excited singlet state of afluorescent dye.

[0008] Next, concerning the mass production method of panels,conventionally a vacuum deposition method has been used. However, thevacuum deposition method cannot be always suitable for mass productionof panels having large areas since they have the problems in that theyrequire a vacuum equipment and it becomes more difficult to forming anorganic thin film so as to have a uniform thickness according as thefilm has a larger area.

[0009] In order to improve the disadvantage, a production method using apolymer light emitting material, that is, an inkjet method and aprinting method have been developed as methods that facilitate theproduction of large area products. In particular, the printing methodcan continuously form a long film so that it is excellent in theproduction of large area products and in mass productivity.

[0010] As described above, in order to obtain an organic light emittingdevice having a high light emission efficiency and having a large area,a phosphorescent polymer material is required. As such phosphorescentpolymer materials, polymers incorporating ruthenium complexes in themain chains or side chains of the polymers are known (Ng, P. K. et al.,Polymer Preprints., Vol. 40(2), page 1212 (1999)). These compounds areionic compounds and application of a voltage thereto causeselectrochemical light emission due to the oxidation reduction reactionat the electrodes. The electrochemical light emission shows an extremelyslow response in the order of minutes so that they are unsuitable forusual display panels.

[0011] In addition, there is a composition of poly(N-vinylcarbazole)mixed or dispersed with a low molecular weight phosphorescent compound,an iridium complex, although it cannot be said to be a polymer materialin a strict sense (P. J. Djurovich et al., Polymer Preprints, Vol.41(1), page 770 (2000)). However, there is a possibility that thismaterial is poor in heat stability as compared with homogeneous polymermaterials and tend to cause phase separation or segregation.

[0012] Japanese Patent Application Laid-open No. 2001-181616, JapanesePatent Application Laid-open No. 2001-181617, and Japanese PatentApplication Laid-open No. 2001-247859 disclose organic light emittingmaterials composed of phosphorescent ortho-metallized palladium complex,ortho-metallized platinum complex and ortho-metallized iridium complex,respectively, and also refer to polymer compounds having these complexstructures as repeating units. However, these publications fail todisclose specific exemplification of the structure and method ofpreparing polymers that are necessary for forming polymers by bindingthe complex structures as the repeating units disclosed in thepublications and discloses no practically usable phosphorescent polymercompounds.

DISCLOSURE OF THE INVENTION

[0013] As described above, there has been no light emitting material fororganic light emitting devices having an external quantum efficiencythat exceeds 5%; which has been conventionally said to be the limitvalue of the external quantum efficiency of fluorescence. In addition,materials having high efficiencies of light emission have been demandedfrom the viewpoint of improvement in durability of the device since theyhave a small energy loss so that heat generation of the device can beprevented. Accordingly, an object of the present invention is toovercome the above-mentioned problems of the prior art and to provide anorganic light emitting device having high luminance and high durabilityand a light emitting material for use therein.

[0014] As a result of extensive studies with a view to solving theabove-mentioned problems, the inventors of the present invention havefound that binding a light emitting substance to a polymer can give riseto light emission of high efficiency from an excited triplet state, thusachieving the present invention.

[0015] The expression “binding to a polymer” as used herein means that alight emitting substance is immobilized by some action of the polymer.The method of immobilization is not particularly limited and includesimmobilization by chemical bonds or physical bonds, such as covalentbond, coordinate bond, formation of charge transfer complex, ion bond,van der Waals force, and host-guest bond, e.g., intercalation.

[0016] In the present invention, a part of the structure of lightemitting substance may forms a part of the polymer whereto the lightemitting substance is bound, or a part of the ligand of the complexbeing a light emitting substance may be incorporated into the polymer.

[0017] Also, the present inventors have found that a polymer lightemitting material obtained by forming a polymerizable compositioncontaining at least one light emitting compound into a film and thenpolymerizing it has good durability and good processability and thatimmobilizing the light emitting substance (light emitting part) with apolymer can give rise to light emission of high efficiency from anexcited triplet state or light emission of high efficiency through anexcited triplet state, thus achieving the present invention.

[0018] That is, the present invention relates to the following lightemitting materials and light emitting devices.

[0019] [1] A polymer light emitting material, wherein the material has alight emitting mechanism based on transition from an excited tripletstate to a ground state or transition through an excited triplet stateto a ground state of an electron energy level, and the materialcomprises a nonionic light emitting part which constitutes a part of thepolymer or is bound to the polymer.

[0020] [2] The polymer light emitting material according to [1], whereinthe light emitting part is formed by binding a metal atom to at leastone site of the polymer.

[0021] [3] The polymer light emitting material according to [2], whereinthe metal atom is bound by one or more covalent bonds and/or one or morecoordinate bonds.

[0022] [4] The polymer light emitting material according to [1], whereinthe light emitting part is a metal complex structure having a metal atomor an organometallic structure having a metal atom.

[0023] [5] The polymer light emitting material according to [2] or [4],wherein the metal atom is a transition metal atom.

[0024] [6] The polymer light emitting material according to [5], whereinthe transition metal atom is a transition metal atom belonging to thesixth period of the periodic table.

[0025] [7] The polymer light emitting material according to [6], whereinthe transition metal atom is iridium.

[0026] [8] The polymer light emitting material according to [6], whereinthe transition metal is platinum.

[0027] [9] The polymer light emitting material according to [2] or [4],wherein the metal atom is a rare earth metal atom.

[0028] [10] The polymer light emitting material according to any one of[1] to [9], wherein the light emitting part is formed by bindingcontaining a coordinate bond formed by a metal atom and a nitrogen atomof the polymer.

[0029] [11] The polymer light emitting material according to [10],wherein the nitrogen atom of the polymer is a nitrogen atom of apyridine skeleton and/or pyrimidine skeleton and/or quinoline skeletonon the side of the polymer.

[0030] [12] The polymer light emitting material according to [10],wherein the nitrogen atom of the polymer is a nitrogen atom of aphenylpyridine skeleton on the side of the polymer.

[0031] [13] The polymer light emitting material according to [10],wherein the nitrogen atom of the polymer is a nitrogen atom of abenzothienyl-pyridine skeleton on the side of the polymer.

[0032] [14] The polymer light emitting material according to [1],comprising a light emitting part that contains a phosphorescent moietyand a fluorescent moiety with fluorescence occurring from thefluorescent moiety through an excited triplet state of thephosphorescent moiety and an excited triplet state of the fluorescentmoiety, wherein at least one of the phosphorescent moiety and thefluorescent moiety constitutes a part of the polymer or is bound to thepolymer.

[0033] [15] The polymer light emitting material according to [1],wherein the material is obtained by polymerizing a polymerizablecomposition containing at least one light emitting compound.

[0034] [16] The polymer light emitting material according to [15],wherein the light emitting compound is a polymerizable light emittingcompound.

[0035] [17] The polymer light emitting material according to [15],wherein the polymer obtained by polymerizing the composition has nocrosslinking structure.

[0036] [18] The polymer light emitting material according to [16],wherein the at least one polymerizable light emitting compound is acrosslinking polymerizable light emitting compound having two or morepolymerizable functional groups and the polymer after the polymerizationis a crosslinked polymer.

[0037] [19] The polymer light emitting material according to any one of[15] to [18], wherein the polymerizable composition contains at leastone polymerizable compound other than the light emitting compound.

[0038] [20] The polymer light emitting material according to [19],wherein the at least one polymerizable compound other than the lightemitting compound is a polymerizable electron transporting compound.

[0039] [21] The polymer light emitting material according to [19],wherein at least one polymerizable compound other than the lightemitting compound is a crosslinking polymerizable compound having two ormore polymerizable functional groups.

[0040] [22] The polymer light emitting material according to [15],wherein a light emitting part of the polymer light emitting material isa metal complex structure having a metal atom or an organometallicstructure having a metal atom.

[0041] [23] The polymer light emitting material according to [22],wherein the metal atom is a transition metal atom.

[0042] [24] The polymer light emitting material according to [22],wherein the metal atom is a rare earth metal atom.

[0043] [25] The polymer light emitting material according to any one of[22] to [24], wherein the light emitting part contains a nitrogen atomin a complex structure forming part or in an organometallic structureforming part.

[0044] [26] The polymer light emitting material according to [25],wherein the light emitting part has a pyridine skeleton, a pyrimidineskeleton and/or a quinoline skeleton in a complex structure forming partor in an organometallic structure forming part.

[0045] [27] The polymer light emitting material according to [16],wherein the polymerizable light emitting compound is a polymerizablecompound represented by the formula (C-1) below:

[0046] wherein at least one of A^(c), B^(c), and C^(c) represents asubstituent having a polymerizable functional group, and the remainderof A^(c), B^(c), and C^(c) independently represent a hydrogen atom, ahalogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms; and R¹ to R²¹independently represent a hydrogen atom, a halogen atom, a nitro group,an amino group, a sulfonic acid group, a sulfonic acid ester group, oran organic group having 1 to 20 carbon atoms which may have one or moreheteroatoms.

[0047] [28] The polymer light emitting material according to [16],wherein the polymerizable light emitting compound is a polymerizablecompound represented by the formula (D-1) below:

[0048] wherein at least one of X^(1D), Y^(1D), and Z^(1D) represents asubstituent having a polymerizable functional group, and the remainderof X^(1D), Y^(1D), and Z^(1D) independently represent a hydrogen atom,or an organic group having 1 to 20 carbon atoms which may have one ormore heteroatoms; and R¹ to R¹⁶ independently represent a hydrogen atom,a halogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms.

[0049] [29] The polymer light emitting material according to [16],wherein the polymerizable light emitting compound is a polymerizablecompound represented by the formula (E-1) below:

[0050] wherein X^(E) represents a substituent having a polymerizablefunctional group; R^(1E), R^(2E) and R^(3E) independently represents ahydrogen atom, a halogen atom, or an organic group having 1 to 20 carbonatoms; and R⁴ to R¹⁹ independently represent a hydrogen atom, a halogenatom, a nitro group, an amino group, a sulfonic acid group, a sulfonicacid ester group, or an organic group having 1 to 20 carbon atoms whichmay have one or more heteroatoms.

[0051] [30] The polymer light emitting material according to [16],wherein the polymerizable light emitting compound is a polymerizablecompound represented by the formula (F-1) below:

[0052] wherein at least one of X^(1F), Y^(1F), and Z^(1F) represents asubstituent having a polymerizable functional group, and the remainderof X^(1F), Y^(1F), and Z^(1F) independently represent a hydrogen atom, ahalogen atom, or an organic group having 1 to 20 carbon atoms which mayhave one or more heteroatoms; and R¹ to R¹⁶ independently represent ahydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonicacid group, a sulfonic acid ester group, or an organic group having 1 to20 carbon atoms which may have one or more heteroatoms.

[0053] [31] The polymer light emitting material according to [16],wherein the polymerizable light emitting compound is a polymerizablecompound represented by the formula (G-1) below:

[0054] wherein L represents a monovalent anionic bidentate ligand; X^(G)represents a substituent having a polymerizable functional group; and R¹to R⁷ independently represent a hydrogen atom, a halogen atom, a nitrogroup, an amino group, a sulfonic acid group, a sulfonic acid estergroup, or an organic group having 1 to 20 carbon atoms which may haveone or more heteroatoms.

[0055] [32] A light emitting composition comprising the polymer lightemitting material according to anyone of [1] to [31], and a carriertransporting polymer compound.

[0056] [33] The light emitting composition according to [32], whereinthe carrier transporting polymer compound is a hole transporting polymercompound.

[0057] [34] The light emitting composition according to [32], whereinthe carrier transporting polymer compound is an electron transportingpolymer compound.

[0058] [35] A light emitting composition comprising the light emittingmaterial according to any one of [1] to [31], and a carrier transportinglow molecular weight compound.

[0059] [36] The light emitting composition according to [35], whereinthe carrier transporting low molecular weight compound is a holetransporting low molecular weight compound.

[0060] [37] The light emitting composition according to [35], whereinthe carrier transporting low molecular weight compound is an electrontransporting low molecular weight compound.

[0061] [38] A layer containing a light emitting material for organiclight emitting device, wherein a light emitting material is a polymerlight emitting material described in [1].

[0062] [39] The layer containing a light emitting material for organiclight emitting device according to [38], obtained by forming into a filma polymer light emitting material described in [1].

[0063] [40] The layer containing a light emitting material for organiclight emitting device according to [39], wherein the polymer lightemitting material has no crosslinking structure.

[0064] [41] The layer containing a light emitting material for organiclight emitting device according to [38], wherein the polymer lightemitting material is obtained by forming a polymerizable compositioncontaining at least one light emitting compound into a film and thenpolymerizing it.

[0065] [42] The layer containing a light emitting material for organiclight emitting device according to [41], wherein the polymer lightemitting material has no crosslinking structure.

[0066] [43] The layer containing a light emitting material for organiclight emitting device according to [41], wherein the polymer lightemitting material has a crosslinking structure.

[0067] [44] An organic light emitting device comprising the polymerlight emitting material according to any one of [1] to [31].

[0068] [45] The organic light emitting device according to [44],comprising a light emitting layer comprising the polymer light emittingmaterial described in any one of [1] to [31] having both sides or oneside thereof an electron transporting layer of a coated type, and/or ahole transporting layer of a coated type.

[0069] Furthermore, the present invention relates to novel polymerizablecompounds, production methods and polymers obtained by polymerizing thepolymerizable compounds represented by [A1] to [A3], [B1] to [B2], [C1]to [C60], [D1] to [D38], [E1] to [E34], [F1] to [F38], and [G1] to [G26]below.

[0070] [A1] A polymerizable compound which is a metal complex having oneor more ligands, wherein at least one ligand is a bidentate ligandhaving pyridine ring which may have one or more substituents, and atleast one ligand including the bidentate ligand above has apolymerizable functional group.

[0071] [A2] The polymerizable compound according to [A1], wherein ametal of the metal complex is iridium.

[0072] [A3] The polymerizable compound according to [A1] or [A2],wherein the bidentate ligand having pyridine ring is phenylpyridine orbenzothienylpyridine.

[0073] [B1] A polymerizable compound represented by the formula (B-1):

[0074] wherein Q represents a bidentate ligand having one or morepolymerizable functional groups, and R¹ to R¹⁶ independently represent ahydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonicacid group, a sulfonic acid ester group, or an organic group having 1 to20 carbon atoms which may have one or more heteroatoms.

[0075] [B2] A polymerizable compound represented by the formula (B-2):

[0076] wherein Q represents a bidentate ligand having one or morepolymerizable functional groups, and R¹ to R¹⁶ independently represent ahydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonicacid group, a sulfonic acid ester group, or an organic group having 1 to20 carbon atoms which may have one or more heteroatoms.

[0077] [C1] A polymerizable compound represented by the formula (C-1):

[0078] wherein at least one of A^(c), B^(c), and C^(c) represents asubstituent having a polymerizable functional group, and the remainderof A^(c), B^(c), and C^(c) independently represent a hydrogen atom, ahalogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms; and R¹ to R²¹independently represent a hydrogen atom, a halogen atom, a nitro group,an amino group, a sulfonic acid group, a sulfonic acid ester group, oran organic group having 1 to 20 carbon atoms which may have one or moreheteroatoms.

[0079] [C2] The polymerizable compound according to [C1] above, whereinat least one of A^(c), B^(c), and C^(c) in the formula (C-1) is asubstituent having an acrylate group or a methacrylate group.

[0080] [C3] The polymerizable compound according to [C2] above, whereinone of A^(c), B^(c), and C^(c) in the formula (C-1) is a substituenthaving an acrylate group or a methacrylate group.

[0081] [C4] A polymerizable compound represented by the formula (C-2):

[0082] wherein R¹ and R² independently represent a hydrogen atom, ahalogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms.

[0083] [C5] The polymerizable compound according to [C4] above, whereinboth R¹ and R² in the formula (C-2) are a hydrogen atom.

[0084] [C6] A polymerizable compound represented by the formula (C-3):

[0085] wherein R¹ and R² independently represent a hydrogen atom, ahalogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms.

[0086] [C7] The polymerizable compound according to [C6] above, whereinboth R¹ and R² in the formula (C-3) are a hydrogen atom.

[0087] [C8] The polymerizable compound according to [C2] above, whereintwo of A^(c), B^(c), and C^(c) in the formula (C-1) are substituentshaving an acrylate group or a methacrylate group.

[0088] [C9] A polymerizable compound represented by the formula (C-4):

[0089] wherein R¹ represents a hydrogen atom, a halogen atom, a nitrogroup, an amino group, a sulfonic acid group, a sulfonic acid estergroup, or an organic group having 1 to 20 carbon atoms which may haveone or more heteroatoms.

[0090] [C10] The polymerizable compound according to [C9] above, whereinR¹ in the formula (C-4) is a hydrogen atom.

[0091] [C11] A polymerizable compound represented by the formula (C-5):

[0092] wherein R¹ represents a hydrogen atom, a halogen atom, a nitrogroup, an amino group, a sulfonic acid group, a sulfonic acid estergroup, or an organic group having 1 to 20 carbon atoms which may haveone or more heteroatoms.

[0093] [C12] The polymerizable compound according to [C11] above,wherein R¹ in the formula (C-5) is a hydrogen atom.

[0094] [C13] The polymerizable compound according to [C2] above, whereinall of A^(c), B^(c), and C^(c) in the formula (C-1) are a substituenthaving an acrylate group or a methacrylate group.

[0095] [C14] A polymerizable compound represented by the formula (C-6):

[0096] [C15] A polymerizable compound represented by the formula (C-7):

[0097] [C16] A polymer obtained by polymerizing the polymerizablecompound represented by the formula (C-1):

[0098] wherein at least one of A^(c), B^(c), and C^(c) represents asubstituent having a polymerizable functional group, and the remainderof A^(c), B^(c), and C^(c) independently represent a hydrogen atom, ahalogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms; and R¹ to R²¹independently represent a hydrogen atom, a halogen atom, a nitro group,an amino group, a sulfonic acid group, a sulfonic acid ester group, oran organic group having 1 to 20 carbon atoms which may have one or moreheteroatoms.

[0099] [C17] The polymer according to [C16] above, wherein at least oneof A^(c), B^(c), and C^(c) in the formula (C-1) is a substituent havingan acrylate group or a methacrylate group.

[0100] [C18] The polymer according to [C17] above, wherein one of A^(c),B^(c), and C^(c) in the formula (C-1) is a substituent having anacrylate group or a methacrylate group.

[0101] [C19] A polymer obtained by polymerizing the polymerizablecompound represented by the formula (C-2):

[0102] wherein R¹ and R² independently represent a hydrogen atom, ahalogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms.

[0103] [C20] The polymer according to [C19] above, wherein both R¹ andR² in the formula (C-2) are a hydrogen atom.

[0104] [C21] A polymer obtained by polymerizing the polymerizablecompound represented by the formula (C-3):

[0105] wherein R¹ and R² independently represent a hydrogen atom, ahalogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms.

[0106] [C22] The polymer according to [C21] above, wherein both R¹ andR² in the formula (C-3) are a hydrogen atom.

[0107] [C23] The polymer according to [C17] above, wherein two of A^(c),B^(c), and C^(c) in the formula (C-1) are substituents having anacrylate group or a methacrylate group.

[0108] [C24] A polymer obtained by polymerizing the polymerizablecompound represented by the formula (C-4):

[0109] wherein R¹ represents a hydrogen atom, a halogen atom, a nitrogroup, an amino group, a sulfonic acid group, a sulfonic acid estergroup, or an organic group having 1 to 20 carbon atoms which may haveone or more heteroatoms.

[0110] [C25] The polymer according to [C24] above, wherein R¹ in theformula (C-4) is a hydrogen atom.

[0111] [C26] A polymer obtained by polymerizing the polymerizablecompound represented by the formula (C-5):

[0112] wherein R¹ represents a hydrogen atom, a halogen atom, a nitrogroup, an amino group, a sulfonic acid group, a sulfonic acid estergroup, or an organic group having 1 to 20 carbon atoms which may haveone or more heteroatoms.

[0113] [C27] The polymer according to [C26] above, wherein R¹ in theformula (C-5) is a hydrogen atom.

[0114] [C28] The polymer according to [C17] above, wherein all of A^(c),B^(c), and C^(c) in the formula (C-1) are a substituent having anacrylate group or a methacrylate group.

[0115] [C29] A polymer obtained by polymerizing the polymerizablecompound represented by the formula (C-6):

[0116] [C30] A polymer obtained by polymerizing the polymerizablecompound represented by the formula (C-7):

[0117] [C31] A copolymer comprising at least one of monomer unitsderived from the polymerizable compounds represented by any one of theformulae (C-1) to (C-7).

[0118] [C32] A method of producing a polymerizable compound containing amononuclear iridium complex, comprising reacting a binuclear iridiumcomplex represented by the formula (C-8) with a phenylpyridinederivative represented by the formula (C-9), and then reacting areactive substituent of the reaction product with a compound having apolymerizable functional group;

[0119] wherein X^(c) and Y^(c) independently represent a reactivesubstituent, or a hydrogen atom, a halogen atom, a nitro group, an aminogroup, a sulfonic acid group, a sulfonic acid ester group, or an organicgroup having 1 to 20 carbon atoms which may have one or moreheteroatoms, and R¹ to R²⁸ independently represent a hydrogen atom, ahalogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms;

[0120] wherein Z^(c) represents a reactive substituent., or a hydrogenatom, a halogen atom, a nitro group, an amino group, a sulfonic acidgroup, a sulfonic acid ester group, or an organic group having 1 to 20carbon atoms which may have one or more heteroatoms, and R¹ to R⁷independently represent a hydrogen atom, a halogen atom, a nitro group,an amino group, a sulfonic acid group, a sulfonic acid ester group, oran organic group having 1 to 20 carbon atoms which may have one or moreheteroatoms, provided that at least one of X^(c) and Y^(c) in theformula (C-8) and Z^(c) in the formula (C-9) is a reactive substituent.

[0121] [C33] The method of producing a polymerizable compound containinga mononuclear iridium complex according to [C32] above, wherein X^(c)and Y^(c) in the formula (C-8) independently represent a hydrogen atom,a halogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms, and Z^(c) in the formula(C-9) represents a reactive substituent.

[0122] [C34] The method of producing a polymerizable compound containinga mononuclear iridium complex according to [C33] above, wherein Z^(c) inthe formula (C-9) represents a hydroxyl group.

[0123] [C35] The method of producing a polymerizable compound containinga mononuclear iridium complex according to [C34] above, wherein thecompound having a polymerizable functional group is an acid halide.

[0124] [C36] The method of producing a polymerizable compound containinga mononuclear iridium complex according to [C34] above, wherein thecompound having a polymerizable functional group is an isocyanatecompound.

[0125] [C37] The method of producing a polymerizable compound containinga mononuclear iridium complex according to [C32] above, wherein X^(c)and Y^(c) in the formula (C-8) independently represent a reactivesubstituent, and Z^(c) in the formula (C-9) represents a hydrogen atom,a halogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms.

[0126] [C38] The method of producing a polymerizable compound containinga mononuclear iridium complex according to [C37] above, wherein Z^(c) inthe formula (C-9) represents a hydroxyl group.

[0127] [C39] The method of producing a polymerizable compound containinga mononuclear iridium complex according to [C38] above, wherein thecompound having a polymerizable functional group is an acid halide.

[0128] [C40] The method of producing a polymerizable compound containinga mononuclear iridium complex according to [C37] above, wherein thecompound having a polymerizable functional group is an isocyanatecompound.

[0129] [C41] A method of producing a polymerizable compound containingan iridium complex part, comprising reacting an iridium complexrepresented by the formula (C-10) with a compound having polymerizablefunctional group in a predetermined molar ratio, and optionally reactingan unreacted reactive substituent, if any, of the obtained product withan unpolymerizable compound;

[0130] wherein X^(c) represents a reactive substituent, and R¹ to R²¹independently represent a hydrogen atom, a halogen atom, a nitro group,an amino group, a sulfonic acid group, a sulfonic acid ester group, oran organic group having 1 to 20 carbon atoms which may have one or moreheteroatoms.

[0131] [C42] The method of producing a polymerizable compound containingan iridium complex part according to [C41] above, wherein the molarratio of the iridium complex represented by the formula (C-10) to thecompound having a polymerizable functional group is 1:(0.5 to 1.5).

[0132] [C43] The method of producing a polymerizable compound containingan iridium complex part according to [C42] above, wherein the reactivesubstituent in the formula (C-10) is a hydroxyl group. [C44] The methodof producing a polymerizable compound containing an iridium complex partaccording to [C43] above, wherein the compound having a polymerizablefunctional group is an acid halide.

[0133] [C45] The method of producing a polymerizable compound containingan iridium complex part according to [C43] above, wherein the compoundhaving a polymerizable functional group is an isocyanate compound.

[0134] [C46] The method of producing a polymerizable compound containingan iridium complex part according to [C41] above, wherein the molarratio of the iridium complex represented by the formula (C-10) to thecompound having a polymerizable functional group is 1:(1.5 to 2.5).

[0135] [C47] The method of producing a polymerizable compound containingan iridium complex part according to [C46] above, wherein the reactivesubstituent in the formula (C-10) is a hydroxyl group.

[0136] [C48] The method of producing a polymerizable compound containingan iridium complex part according to [C47] above, wherein the compoundhaving a polymerizable functional group is an acid halide.

[0137] [C49] The method of producing a polymerizable compound containingan iridium complex part according to [C47] above, wherein the compoundhaving a polymerizable functional group is an isocyanate compound.

[0138] [C50] The method of producing a polymerizable compound containingan iridium complex part according to [C41] above, wherein the molarratio of the iridium complex represented by the formula (C-10) to thecompound having a polymerizable functional group is 1:(2.5 or more).

[0139] [C51] The method of producing a polymerizable compound containingan iridium complex part according to [C50] above, wherein the reactivesubstituent in the formula (C-10) is a hydroxyl group.

[0140] [C52] The method of producing a polymerizable compound containingan iridium complex part according to [C51] above, wherein the compoundhaving a polymerizable functional group is an acid halide.

[0141] [C53] The method of producing a polymerizable compound containingan iridium complex part according to [C51] above, wherein the compoundhaving a polymerizable functional group is an isocyanate compound.

[0142] [C54] A compound represented by the formula (C-11):

[0143] wherein at least one of X^(c), Y^(c), and Z^(c) represents ahydroxyl group, and the remainder of X^(c), Y^(c), and Z^(c)independently represent a hydrogen atom, a halogen atom, a nitro group,an amino group, a sulfonic acid group, a sulfonic acid ester group, oran organic group having 1 to 20 carbon atoms which may have one or moreheteroatoms; and R¹ to R²¹ independently represent a hydrogen atom, ahalogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms.

[0144] [C55] The compound according to [C54] above, wherein one ofX^(c), Y^(c), and Z^(c) in the formula (C-11) is a hydroxyl group.

[0145] [C56] A compound represented by the formula (C-12):

[0146] [C57] The compound according to [C54] above, wherein two ofX^(c), Y^(c), and Z^(c) in the formula (C-11) are a hydroxyl group.

[0147] [C58] A compound represented by the formula (C-13):

[0148] [C59] The compound according to [C54] above, wherein all ofX^(c), Y^(c), and Z^(c) in the formula (C-11) are a hydroxyl group.

[0149] [C60] A compound represented by the formula (C-14):

[0150] [D1] A polymerizable compound represented by the formula (D-1):

[0151] wherein at least one of X^(1D), Y^(1D), and Z^(1D) represents asubstituent having a polymerizable functional group, and the remainderof X^(1D), Y^(1D), and Z^(1D) independently represent a hydrogen atom,or an organic group having 1 to 20 carbon atoms which may have one ormore heteroatoms, and R¹ to R¹⁶ independently represent a hydrogen atom,a halogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms.

[0152] [D2] The polymerizable compound according to [D1] above, whereinone of X^(1D) or Z^(1D) in the formula (D-1) is a substituent having apolymerizable functional group.

[0153] [D3] A polymerizable compound represented by the formula (D-2):

[0154] wherein X^(1D) represents a substituent having a polymerizablefunctional group, and Q^(1D) and Q^(2D) independently represent ahydrogen atom, or an organic group having 1 to 20 carbon atoms which mayhave one or more heteroatoms.

[0155] [D4] The polymerizable compound according to any one of [D1] to[D3] above, wherein the polymerizable functional group is a group havinga carbon-carbon double bond.

[0156] [D5] A polymerizable compound represented by the formula (D-3):

[0157] [D6] The polymerizable compound according to any one of [D1] to[D3] above, wherein the polymerizable functional group is a styrylgroup.

[0158] [D7] A polymerizable compound represented by the formula (D-4):

[0159] [D8] The polymerizable compound according to any one of [D1] to[D3] above, wherein the polymerizable functional group is an acrylategroup or a methacrylate group.

[0160] [D9] A polymerizable compound represented by the formula (D-5):

[0161] wherein R represents a hydrogen atom or a methyl group.

[0162] [D10] A polymerizable compound represented by the formula (D-6):

[0163] wherein R represents a hydrogen atom or a methyl group.

[0164] [D7] A polymerizable compound represented by the formula (D-7):

[0165] wherein R represents a hydrogen atom or a methyl group.

[0166] [D12] A polymerizable compound represented by the formula (D-8):

[0167] wherein R represents a hydrogen atom or a methyl group.

[0168] [D13] A polymerizable compound represented by the formula (D-9):

[0169] wherein R represents a hydrogen atom or a methyl group.

[0170] [D14] A polymerizable compound represented by the formula (D-10):

[0171] wherein R represents a hydrogen atom or a methyl group.

[0172] [D15] A polymerizable compound represented by the formula (D-11):

[0173] wherein R represents a hydrogen atom or a methyl group.

[0174] [D16] A polymerizable compound represented by the formula (D-12):

[0175] wherein R represents a hydrogen atom or a methyl group.

[0176] [D17] A polymerizable compound represented by the formula (D-13):

[0177] [D18] The polymerizable compound according to [D1] above, whereinY^(1D) in the formula (D-1) is a substituent having a polymerizablefunctional group.

[0178] [D19] A polymerizable compound represented by the formula (D-14):

[0179] wherein Y^(1D) represents a substituent having a polymerizablefunctional group, and Q²D and Q³D independently represent a hydrogenatom, or an organic group having 1 to 20 carbon atoms which may have oneor more heteroatoms.

[0180] [D20] The polymerizable compound according to [D18] or [D19]above, wherein the polymerizable functional group is a group having acarbon-carbon double bond.

[0181] [D21] The polymerizable compound according to [D18] or [D19]above, wherein the polymerizable functional group is a styryl group.

[0182] [D22] The polymerizable compound according to [D18] or [D19]above, wherein the polymerizable functional group is an acrylate groupor a methacrylate group.

[0183] [D23] A polymerizable compound represented by the formula (D-15):

[0184] wherein R represents a hydrogen atom or a methyl group.

[0185] [D24] A polymerizable compound represented by the formula (D-16):

[0186] wherein R represents a hydrogen atom or a methyl group.

[0187] [D25] A method of producing a polymerizable compound containing amononuclear iridium complex part, comprising reacting a binucleariridium complex represented by the formula (D-17) with a compound havinga polymerizable functional group represented by the formula (D-18)below:

[0188] wherein R¹ to R³² independently represent a hydrogen atom, ahalogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms;

[0189] wherein at least one of X^(1D), Y^(1D), and Z^(1D) represents asubstituent having a polymerizable functional group, and the remainderof X^(1D), Y^(1D), and Z^(1D) independently represent a hydrogen atom,or an organic group having 1 to 20 carbon atoms which may have one ormore heteroatoms.

[0190] [D26] The method of producing a polymerizable compound containinga mononuclear iridium complex part according to [D25] above, whereinX^(1D) or Z^(1D) in the formula (D-18) is a substituent having apolymerizable functional group.

[0191] [D27] The method of producing a polymerizable compound containinga mononuclear iridium complex part according to [D25] above, whereinY^(1D) in the formula (D-18) is a substituent having a polymerizablefunctional group.

[0192] [D28] A method of producing a polymerizable compound containing amononuclear iridium complex part, comprising reacting a binucleariridium complex represented by the formula (D-17) with a compound havinga polymerizable functional group represented by the formula (D-19) belowand then reacting a reactive substituent of the obtained mononucleariridium complex with a compound having a polymerizable functional group:

[0193] wherein R¹ to R³² independently represent a hydrogen atom, ahalogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms;

[0194] wherein at least one of X^(2D), Y^(2D), and Z^(2D) represents asubstituent having a polymerizable functional group, and the remainderof X^(2D), Y^(2D), and Z^(2D) independently represent a hydrogen atom,or an organic group having 1 to 20 carbon atoms which may have one ormore heteroatoms.

[0195] [D29] The method of producing a polymerizable compound containinga mononuclear iridium complex part according to [D28] above, whereinX^(2D) or Z^(2D) in the formula (D-19) is a substituent having ahydroxyl group.

[0196] [D30] The method of producing a polymerizable compound containinga mononuclear iridium complex part according to [D28] above, whereinY^(2D) in the formula (D-19) is a substituent having a hydroxyl group.

[0197] [D31] A compound represented by the formula (D-20):

[0198] wherein at least one of X^(2D), Y^(2D), and Z^(2D) represents asubstituent having a hydroxyl group, and the remainder of X^(2D),Y^(2D), and Z^(2D) independently represent a hydrogen atom, or anorganic group having 1 to 20 carbon atoms which may have one or moreheteroatoms; and R¹ to R¹⁶ independently represent a hydrogen atom, ahalogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms.

[0199] [D32] The compound according to [D31] above, wherein X^(2D) orZ^(2D) in the formula (D-20) is a substituent having a hydroxyl group.

[0200] [D33] A compound represented by the formula (D-21):

[0201] wherein n is 0 or an integer of 1 to 20, and Q^(1D) and Q^(2D)independently represent a hydrogen atom, or an organic group having 1 to20 carbon atoms which may have one or more heteroatoms.

[0202] [D34] A compound represented by the formula (D-22):

[0203] wherein n is 0 or an integer of 1 to 20, and Q^(1D) and Q^(2D)independently represent a hydrogen atom, or an organic group having 1 to20 carbon atoms which may have one or more heteroatoms.

[0204] [D35] The compound according to [D31] above, wherein Y^(2D) inthe formula (D-20) is a substituent having a hydroxyl group.

[0205] [D36] A compound represented by the formula (D-23):

[0206] wherein n is 0 or an integer of 1 to 20, and Q^(2D) and Q^(3D)independently represent a hydrogen atom, or an organic group having 1 to20 carbon atoms which may have one or more heteroatoms.

[0207] [D37] A polymer of the polymerizable compound according to anyone of [D1] to [D24] above.

[0208] [D38] A polymer obtained by polymerizing a composition containingat least one of the polymerizable compounds according to [D1] to [D24]above.

[0209] [E1] A polymerizable compound represented by the formula (E-1):

[0210] wherein X^(E) represents a substituent having a polymerizablefunctional group; R^(1E), R^(2E) and R^(3E) independently represent ahydrogen atom, a halogen atom, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms; and R⁴ to R¹⁹independently represent a hydrogen atom, a halogen atom, a nitro group,an amino group, a sulfonic acid group, a sulfonic acid ester group, oran organic group having 1 to 20 carbon atoms which may have one or moreheteroatoms.

[0211] [E2] The polymerizable compound according to [E1] above, whereinthe polymerizable functional group of X^(E) in the formula (E-1) is agroup having a carbon-carbon double bond.

[0212] [E3] A polymerizable compound represented by the formula (E-2):

[0213] wherein X^(E) represents a substituent having a polymerizablefunctional group.

[0214] [E4] The polymerizable compound according to [E1] or [E3] above,wherein the polymerizable functional group is an acryloyloxy group or amethacryloyloxy group.

[0215] [E5] The polymerizable compound according to [E1] or [E3] above,wherein the polymerizable functional group of X^(E) in the formula (E-1)or (E-2) is a methacryloyloxy group.

[0216] [E6] A polymerizable compound represented by the formula (E-3):

[0217] [E7] The polymerizable compound according to [E1] or [E3] above,wherein the polymerizable functional group of X^(E) in the formula (E-1)or (E-2) is a methacryloyloxymethyl group.

[0218] [E8] A polymerizable compound represented by the formula (E-4):

[0219] [E9] The polymerizable compound according to [E1] or [E3] above,wherein the polymerizable functional group of X^(E) in the formula (E-1)or (E-2) is a methacryloyloxyethyl-carbamoyloxymethyl group.

[0220] [E10] A polymerizable compound represented by the formula (E-5):

[0221] [E11] The polymerizable compound according to [E1] or [E3] above,wherein the polymerizable functional group of X^(E) in the formula (E-1)or (E-2) is a methacryloyloxyethyloxycarbonyl group.

[0222] [E12] A polymerizable compound represented by the formula (E-6):

[0223] [E13] The polymerizable compound according to [E1] or [E3] above,wherein the polymerizable functional group is a styryl group.

[0224] [E14] The polymerizable compound according to [E1] or [E3] above,wherein the polymerizable functional group of X^(E) in the formula (E-1)or (E-2) is a vinylbenzyloxy group.

[0225] [E15] A polymerizable compound represented by the formula (E-7):

[0226] [E16] A polymerizable compound represented by the formula (E-8):

[0227] [E17] A method of producing a polymerizable compound containing amononuclear iridium complex part, comprising reacting a binucleariridium complex represented by the formula (E-9) with a picolinic acidderivative represented by the formula (E-10) and then reacting theobtained reaction product with a compound having both a polymerizablefunctional group and a functional group capable of reacting with andbonding the reactive substituent Y^(E) derived from a compoundrepresented by the formula (E-10) below:

[0228] wherein R⁴ to R¹⁹ independently represent a hydrogen atom, ahalogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms;

[0229] wherein Y^(E) represents a reactive substituent; and R^(1E),R^(2E) and R^(3E) independently represent a hydrogen atom, a halogenatom, or an organic group having 1 to 20 carbon atoms which may have oneor more heteroatoms.

[0230] [E18] The method of producing a polymerizable compound containinga mononuclear iridium complex part according to [E17] above, whereinY^(E) in the formula (E-10) is a group having an active hydrogen.

[0231] [E19] The method of producing a polymerizable compound containinga mononuclear iridium complex part according to [E17] above, whereinY^(E) in the formula (E-10) is a hydroxyl group or a hydroxymethylgroup.

[0232] [E20] The method of producing a polymerizable compound containinga mononuclear iridium complex part according to [E19] above, wherein thecompound having both a polymerizable functional group and a functionalgroup capable of reacting with and bonding the reactive substituentY^(E) is an acid chloride compound having a polymerizable functionalgroup.

[0233] [E21] The method of producing a polymerizable compound containinga mononuclear iridium complex part according to [E19] above, wherein thecompound having both a polymerizable functional group and a functionalgroup capable of reacting with and bonding the reactive substituentY^(E) is an alkyl halide compound having a polymerizable functionalgroup.

[0234] [E22] The method of producing a polymerizable compound containinga mononuclear iridium complex part according to [E18] or [E19] above,wherein the compound having both a polymerizable functional group and afunctional group capable of reacting with and bonding the reactivesubstituent Y^(E) is an isocyanate compound having a polymerizablefunctional group.

[0235] [E23] The method of producing a polymerizable compound containinga mononuclear iridium complex part according to [E17] above, whereinY^(E) in the formula (E-10) is a carboxyl group.

[0236] [E24] The method of producing a polymerizable compound containinga mononuclear iridium complex part according to [E23] above, wherein thecompound having both a polymerizable functional group and a functionalgroup capable of reacting with and bonding the reactive substituentY^(E) is a compound having a hydroxyl group and a polymerizablefunctional group.

[0237] [E25] A method of producing a polymerizable compound containing amononuclear iridium complex part, comprising reacting a binucleariridium complex represented by the formula (E-9) and a picolinic acidderivative represented by the formula (E-11):

[0238] wherein R⁴ to R¹⁹ independently represent a hydrogen atom, ahalogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms;

[0239] wherein X^(E) represents a substituent having a polymerizablefunctional group, and R^(1E), R^(2E) and R^(3E) independently representa hydrogen atom, a halogen atom, or an organic group having 1 to 20carbon atoms which may have one or more heteroatoms.

[0240] [E26] The method of producing a polymerizable compound containinga mononuclear iridium complex part according to [E25] above, whereinX^(E) in the formula (E-11) is any one member selected from the groupconsisting of a methacryloyloxy group, a methacryloyloxymethyl group, amethacryloyloxyethylcarbamoyloxymethyl group, amethacryloyloxyethyloxycarbonyl group, and a vinylbenzyloxy group.

[0241] [E27] A compound represented by the formula (E-12):

[0242] wherein Y^(E) represents a reactive substituent, R^(1E), R^(2E)and R^(3E) independently represent a hydrogen atom, a halogen atom, oran organic group having 1 to 20 carbon atoms which may have one or moreheteroatoms, and R⁴ to R¹⁹ independently represent a hydrogen atom, ahalogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms.

[0243] [E28] The compound according to [E27] above, wherein Y^(E) in theformula (E-12) is a hydroxyl group.

[0244] [E29] A compound represented by the formula (E-13):

[0245] [E30] A compound represented by the formula (E-14):

[0246] [E31] A compound represented by the formula (E-15):

[0247] [E32] A polymerizable composition containing the polymerizablecompound according to any one of [E1] to [E16] above.

[0248] [E33] A polymer of the polymerizable compound according to anyone of [E1] to [E16].

[0249] [E34] A polymer obtained by polymerizing the polymerizablecomposition according to [E32] above.

[0250] [F1] A polymerizable compound represented by the formula (F-1):

[0251] wherein at least one of X^(1F), Y^(1F), and Z^(1F) represents asubstituent having a polymerizable functional group, and the remainderof X^(1F), Y^(1F), and Z^(1F) independently represent a hydrogen atom, ahalogen atom, or an organic group having 1 to 20 carbon atoms which mayhave one or more heteroatoms; and R¹ to R¹⁶ independently represent ahydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonicacid group, a sulfonic acid ester group, or an organic group having 1 to20 carbon atoms which may have one or more heteroatoms.

[0252] [F2] The polymerizable compound according to [F1] above, whereineither one of X^(1F) and Z^(1F) is a substituent having a polymerizablefunctional group.

[0253] [F3] A polymerizable compound represented by the formula (F-2):

[0254] wherein X^(1F) represents a substituent having a polymerizablefunctional group, and Q^(1F) and Q^(2F) independently represent ahydrogen atom, a halogen atom, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms.

[0255] [F4] The polymerizable compound according to any one of [F1] to[F3] above, wherein the polymerizable functional group is a group havinga carbon-carbon double bond.

[0256] [F5] A polymerizable compound represented by the formula (F-3):

[0257] wherein n is 0 or an integer of 1 to 20.

[0258] [F6] The polymerizable compound according to any one of [F1] to

[0259] [F3] above, wherein the polymerizable functional group is astyryl group.

[0260] [F7] A polymerizable compound represented by the formula (F-4):

[0261] wherein n is 0 or an integer of 1 to 20.

[0262] [F8] A polymerizable compound represented by the formula (F-5):

[0263] [F9] The polymerizable compound according to any one of [F1] to[F3] above, wherein the polymerizable functional group is an alkenoyloxygroup.

[0264] [F10] A polymerizable compound represented by the formula (F-6):

[0265] wherein n is 0 or an integer of 1 to 20, and A represents anorganic group having 3 to 20 carbon atoms that has an acryloyl group, amethacryloyl group, an acryloyloxy group, or a methacryloyloxy group.

[0266] [F11] A polymerizable compound represented by the formula (F-7):

[0267] wherein R represents a hydrogen atom or a methyl group.

[0268] [F12) A polymerizable compound represented by the formula (F-8):

[0269] wherein R represents a hydrogen atom or a methyl group.

[0270] [F13] A polymerizable compound represented by the formula (F-9):

[0271] wherein n is 0 or an integer of 1 to 20, and A represents anorganic group having 3 to 20 carbon atoms that has an acryloyl group, amethacryloyl group, an acryloyloxy group, or a methacryloyloxy group.

[0272] [F14] A polymerizable compound represented by the formula (F-10):

[0273] wherein R represents a hydrogen atom or a methyl group.

[0274] [F15] A polymerizable compound represented by the formula (F-11):

[0275] wherein R represents a hydrogen atom or a methyl group.

[0276] [F16] The polymerizable compound according to [F1], whereinY^(1F) in the formula (F-1) is a substituent having a polymerizablefunctional group.

[0277] [F17] A polymerizable compound represented by the formula (F-12):

[0278] wherein Y^(1F) represents a substituent having a polymerizablefunctional group, and Q^(2F) and Q^(3F) independently represent ahydrogen atom, a halogen atom, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms.

[0279] [F18] The polymerizable compound according to [F16] or [F17]above, wherein the polymerizable functional group is a group having acarbon-carbon double bond.

[0280] [F19] The polymerizable compound according to [F16] or [F17]above, wherein the polymerizable functional group is a styryl group.

[0281] [F20] The polymerizable compound according to [F16] or [F17]above, wherein the polymerizable functional group is an alkenoyloxygroup.

[0282] [F21] A polymerizable compound represented by the formula (F-13):

[0283] wherein R represents a hydrogen atom or a methyl group.

[0284] [F22] A polymerizable compound represented by the formula (F-14):

[0285] wherein R represents a hydrogen atom or a methyl group.

[0286] [F23] A method of producing a polymerizable compound containing amononuclear iridium complex part, comprising reacting a binucleariridium complex represented by the formula (F-15) below with a compoundhaving a polymerizable functional group represented by the formula(F-16) below:

[0287] wherein R¹ to R¹⁶ independently represent a hydrogen atom, ahalogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms;

[0288] wherein at least one of X^(1F), Y^(1F), and Z^(1F) represents asubstituent having a polymerizable functional group, and the remainderof X^(1F), Y^(1F), and Z^(1F) independently represent a hydrogen atom, ahalogen atom or an organic group having 1 to 20 carbon atoms which mayhave one or more heteroatoms.

[0289] [F24] The method of producing a polymerizable compound containinga mononuclear iridium complex part according to [F23] above, whereinX^(1F) or Z^(1F) in the formula (F-16) is a substituent having apolymerizable functional group.

[0290] [F25] The method of producing a polymerizable compound containinga mononuclear iridium complex part according to [F23] above, whereinY^(1F) in the formula (F-16) is a substituent having a polymerizablefunctional group.

[0291] [F26] A method of producing a polymerizable compound containing amononuclear iridium complex part, comprising reacting a binucleariridium complex represented by the formula (F-15) with a compound havinga reactive substituent represented by the formula (F-17) below, and thenreacting a reactive substituent of the obtained mononuclear iridiumcomplex with a compound having both a polymerizable functional group anda functional group capable of reacting with and bonding to a reactivefunctional substituent derived from the compound of the formula (F-17)(at least one of X^(2F), Y^(2F), and Z^(2F)):

[0292] wherein R¹to R¹⁶independently represent a hydrogen atom, ahalogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms.

[0293] wherein at least one of X^(2F), Y^(2F), and Z^(2F) represents areactive substituent, and the remainder of X^(2F), Y^(2F), and Z^(2F)independently represent a hydrogen atom, a halogen atom or an organicgroup having 1 to 20 carbon atoms which may have one or more heteroatoms

[0294] [F27] The method of producing a polymerizable compound containinga mononuclear iridium complex part according to [F26] above, whereinX^(E), Y^(E) or Z^(E) in the formula (F-17) is a substituent having anactive hydrogen.

[0295] [F28] The method of producing a polymerizable compound containinga mononuclear iridium complex part according to [F26] above, whereinX^(2F) or Z^(2F) in the formula (F-17) is a substituent having ahydroxyl group.

[0296] [F29] The method of producing a polymerizable compound containinga mononuclear iridium complex part according to [F26] above, whereinY^(2F) in the formula (F-17) is a substituent having a hydroxyl group.

[0297] [F30] A compound represented by the formula (F-18):

[0298] wherein at least one of X^(2F), Y^(2F), and Z^(2F) represents asubstituent having a hydroxyl group, and the remainder of X^(2F),Y^(2F), and Z^(2F) independently represent a hydrogen atom, a halogenatom or an organic group having 1 to 20 carbon atoms which may have oneor more heteroatoms; and R¹ to R¹⁶ independently represent a hydrogenatom, a halogen atom, a nitro group, an amino group, a sulfonic acidgroup, a sulfonic acid ester group, or an organic group having 1 to 20carbon atoms which may have one or more heteroatoms.

[0299] [F31] The compound according to [F30] above, wherein X^(2F) orZ^(2F) in the formula (F-18) is a substituent having a hydroxyl group.

[0300] [F32] A compound represented by the formula (F-19):

[0301] wherein is 0 or an integer of 1 to 20, and Q^(1F) and Q^(2F)independently represent a hydrogen atom, a halogen atom, or an organicgroup having 1 to 20 carbon atoms which may have one or moreheteroatoms.

[0302] [F33] A compound represented by the formula (F-20):

[0303] wherein is 0 or an integer of 1 to 20, and Q^(1F) and Q^(2F)independently represent a hydrogen atom, a halogen atom, or an organicgroup having 1 to 20 carbon atoms which may have one or moreheteroatoms.

[0304] [F34] The compound according to [E30] above, wherein Y^(2F) inthe formula (E-18) is a substituent having a hydroxyl group.

[0305] [F35] A compound represented by the formula (F-21):

[0306] wherein n is 0 or an integer of 1 to 20, and Q^(2F) and Q^(3F)independently represent a hydrogen atom, a halogen atom, or an organicgroup having 1 to 20 carbon atoms which may have one or moreheteroatoms.

[0307] [F36] A polymer of the polymerizable compound according to anyone of [F1] to [F22] above.

[0308] [F37] A polymer obtained by polymerizing a polymerizablecomposition containing at least one of the polymerizable compoundsaccording to [F1] to [F22] above.

[0309] [F38] A polymerizable composition containing at least one of thepolymerizable compounds according to [F1] to [F22] above.

[0310] [G1] A polymerizable compound represented by the formula (G-1):

[0311] wherein L represents a monovalent anionic bidentate ligand, X^(G)represents a substituent having a polymerizable functional group, and R¹to R⁷ independently represent a hydrogen atom, a halogen atom, a nitrogroup, an amino group, a sulfonic acid group, a sulfonic acid estergroup, or an organic group having 1 to 20 carbon atoms which may haveone or more heteroatoms.

[0312] [G2] polymerizable compound represented by the formula (G-2):

[0313] wherein A^(1G), A^(2G), and A^(3G) independently represent ahydrogen atom, a halogen atom or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms; X^(G) represents asubstituent having a polymerizable functional group, and R¹ to R⁷independently represent a hydrogen atom, a halogen atom, a nitro group,an amino group, a sulfonic acid group, a sulfonic acid ester group, oran organic group having 1 to 20 carbon atoms which may have one or moreheteroatoms.

[0314] [G3] The polymerizable compound according to [G1] or [G2] above,wherein the polymerizable functional group of X^(G) in the formula (G-1)or (G-2) is a group having a carbon-carbon double bond.

[0315] [G4] The polymerizable compound according to [G1]or [G2] above,wherein X^(G) in the formula (G-1) or (G-2) is any one of amethacryloyloxy group, a methacryloyloxyethylcarbamoyloxy group, and avinylbenzyloxy group.

[0316] [G5] A polymerizable compound represented by the formula (G-3):

[0317] [G6] A polymerizable compound represented by the formula (G-4):

[0318] [G7] A polymerizable compound represented by the formula (G-5):

[0319] [G8] A method of producing a polymerizable compound containing amononuclear iridium complex part, comprising reacting a binucleariridium complex represented by the formula (G-6) with a monovalentanionic bidentate ligand L, and then reacting the reaction product witha compound having both a polymerizable functional group and a functionalgroup capable of reacting with and binding to the substituent Y^(G)having a reactive functional group in the compound represented by theformula (G-6):

[0320] wherein Y^(G) is a substituent having a reactive functionalgroup, and R¹ to R⁷ independently represent a hydrogen atom, a halogenatom, a nitro group, an amino group, a sulfonic acid group, a sulfonicacid ester group, or an organic group having 1 to 20 carbon atoms whichmay have one or more heteroatoms.

[0321] [G9] The method of producing a polymerizable compound containinga mononuclear iridium complex part according to [G8] above, whereinY^(G) in the formula (G-6) is a group having an active hydrogen.

[0322] [G10] The method of producing a polymerizable compound containinga mononuclear iridium complex part according to [G8] above, whereinY^(G) in the formula (G-6) is a substituent having a hydroxyl group.

[0323] [G11] The method of producing a polymerizable compound containinga mononuclear iridium complex part according to [G10] above, wherein thecompound having both a polymerizable functional group and a functionalgroup capable of reacting with and binding to the substituent Y^(G)having a reactive group derived from the compound represented by theformula (G-6) is an acid halide compound having a polymerizablefunctional group or an alkyl halide compound having a polymerizablefunctional group.

[0324] [G12] The method of producing a polymerizable compound containinga mononuclear iridium complex part according to [G9] or [G10] above,wherein the compound having both a polymerizable functional group and afunctional group capable of reacting with and binding to the substituentY^(G) having a reactive group derived from the compound represented bythe formula (G-6) is an isocyanate compound having a polymerizablefunctional group.

[0325] [G13] A method of producing a polymerizable compound containing amononuclear iridium complex part, comprising reacting a binucleariridium complex represented by the formula (G-7) below with a monovalentanionic bidentate ligand L:

[0326] wherein X^(G) is a substituent having a polymerizable functionalgroup, and R¹ to R⁷ independently represent a hydrogen atom, a halogenatom, a nitro group, an amino group, a sulfonic acid group, a sulfonicacid ester group, or an organic group having 1 to 20 carbon atoms whichmay have one or more heteroatoms.

[0327] [G14] A method of producing a polymerizable compound containing amononuclear iridium complex part according to [G13] above, wherein X^(G)in the formula (G-7) is any one of a methacryloyloxy group, amethacryloyloxyethylcarbamoyloxy group, and a vinylbenzyloxy group.

[0328] [G15] A binuclear iridium complex represented by the formula(G-6):

[0329] wherein Y^(G) is a substituent having a reactive functionalgroup, and R¹ to R⁷ independently represent a hydrogen atom, a halogenatom, a nitro group, an amino group, a sulfonic acid group, a sulfonicacid ester group, or an organic group having 1 to 20 carbon atoms whichmay have one or more heteroatoms.

[0330] [G16] The binuclear iridium complex according to [G15], whereinY^(G) in the formula (G-6) is a hydroxyl group.

[0331] [G17] A binuclear iridium complex represented by the formula(G-8):

[0332] [G18] A compound represented by the formula (G-9):

[0333] wherein L represents a monovalent anionic bidentate ligand, Y^(G)represents a substituent having a reactive functional group, and R¹ toR⁷ independently represent a hydrogen atom, a halogen atom, a nitrogroup, an amino group, a sulfonic acid group, a sulfonic acid estergroup, or an organic group having 1 to 20 carbon atoms which may haveone or more heteroatoms.

[0334] [G19] A compound represented by the formula (G-10):

[0335] wherein A^(1G), A^(2G), and A^(3G) independently represent ahydrogen atom, a halogen-atom or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms, Y^(G) represents asubstituent having a reactive functional group, and R¹ to R¹⁷independently represent a hydrogen atom, a halogen atom, a nitro group,an amino group, a sulfonic acid group, a sulfonic acid ester group, oran organic group having 1 to 20 carbon atoms which may have one or moreheteroatoms.

[0336] [G20] The compound according to [G18] or [G19] above, whereinY^(G) in the formula (G-9) or (G-10) is a hydroxyl group.

[0337] [G21] A compound represented by the formula (G-11):

[0338] [G22] A binuclear iridium complex represented by the formula(G-7):

[0339] wherein X^(G) represents a substituent having a polymerizablefunctional group, and R¹ to R⁷ independently represent a hydrogen atom,a halogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms.

[0340] [G23] The binuclear iridium complex according to [G22] above,wherein X^(G) in the formula (G-7) is any one of a methacryloyloxygroup, a methacryloyloxyethylcarbamoyloxy group, and a vinylbenzyloxygroup.

[0341] [G24] A composition containing the polymerizable compoundaccording to any one of [G1] to [G7] above.

[0342] [G25] A polymer of the polymerizable compound according to anyone of [G1] to [G7] above.

[0343] [G26] A polymer obtained by polymerizing a composition containingthe polymerizable compound according to any one of [G1] to [G7].

BRIEF DESCRIPTION OF THE DRAWING

[0344]FIG. 1 is a cross-sectional view showing an example of an organiclight emitting device of the present invention.

MODE OF THE INVENTION

[0345] Hereinafter, modes of the present invention will be describedwith reference to the attached drawing.

[0346]FIG. 1 is a cross-sectional view showing an example of theconstruction of the organic light emitting device of the presentinvention, which includes a hole transport layer 3, a light emittinglayer 4 and an electron transport layer 5 provided in the order citedbetween an anode 2 provided on a transparent substrate 1 and a cathode6. The construction of the organic light emitting device is not limitedto the example shown in FIG. 1 and may be one that has provided betweenthe anode and the cathode in the order cited either (1) a hole transportlayer/a light emitting layer or (2) a light emitting layer/an electrontransport layer. Alternatively, the construction of the organic lightemitting device of the present invention may have only one layer fromany one of (3) a layer containing a hole transporting material, a lightemitting material and an electron transporting material, (4) a layercontaining a hole transporting material and a light emitting material,(5) a layer containing a light emitting material and an electrontransporting material, and (6) a layer containing only a light emittingmaterial. Furthermore, although the light emitting layer shown in FIG. 1consists of one layer, it may consist of two or more laminated layers.

[0347] In the present invention, the light emitting part means a parthaving a molecular structure that emits light from an excited tripletstate, i.e., a phosphorescent emissive part, or a part having amolecular structure that emits light through an excited triplet state(hereinafter, referred to as a “part emits light through an excitedtriplet state”). The light emitting parts are characterized byconstituting a part of a polymer or being bonded to a polymer. The partthat emits light through an excited triplet state refers to a systemthat consists of two constituent parts in which energy transfer occursfrom an excited triplet state of the constituent part corresponding tothe phosphorescent emissive, the first organic compound to an excitedtriplet state of the fluorescent emissive, the second organic compound,followed by fluorescent emission through the constituent partcorresponding to the second organic compound, as disclosed in JapanesePatent Application Laid-open No. 2002-050483.

[0348] In the case where the organic light emitting device of thepresent invention contains the part that emits through an excitedtriplet state as described above, it is preferred that at least one ofthe phosphorescent emissive part and the fluorescent emissive partconstitutes a part of a polymer or is bonded to a polymer. In this case,the phosphorescent emissive part and/or fluorescent emissive part thatconstitutes a part of a polymer or is bonded to a polymer may form themain chain of the polymer or a side chain of the polymer (which means apendant group formed by a functional group or the like pending from themain chain but may also be a long chain branch).

[0349] The quantum efficiency of the phosphorescent emissive part in anexcited triplet state is preferably 0.1 or more, more preferably 0.3 ormore and particularly preferably 0.5 or more. The compound having highquantum efficiency in an excited triplet state that can be used for thephosphorescent emissive part includes, for example, a metal complex andan organometallic compound. Specific examples of the metal complex andthe organometallic compound include transition metal complexes such asiridium complexes and platinum complexes, organometallic compoundscontaining a transition metal such as organometallic iridium compoundsand organometallic platinum compounds and derivatives thereof. Thesecomplexes are preferred in that they have relatively stable excitedtriplet states even at room temperatures. Further, they are preferredsince they can be readily obtained by coordinating a polymer having afunctional group capable of being coordinated to a transition metal atomas will be described later. Other compounds having high quantumefficiencies in an excited triplet state that can be used for thephosphorescent emissive part may be selected from the compoundsdescribed in, for example, “Handbook of Photochemistry, Second Edition(Steven L. Murov, et al., Marcel Dekker Inc., 1993).

[0350] The transition metals used for the above-mentioned transitionmetal complexes and organometallic compounds containing a transitionmetal include elements from Atomic No. 21, Sc, to Atomic No. 30, Zn inthe first transient element series, from Atomic No. 39, Y to Atomic No.48, Cd in the second transient element series, and from Atomic No. 72,Hf to Atomic No. 80, Hg, in the third transient element series of theperiodic table.

[0351] Other specific examples of the metal complex and theorganometallic compound that emit through an excited triplet stateinclude rare earth metal complexes and organometallic compoundscontaining a rare earth metal. The rare earth metals used for the rareearth metal complexes and the organometallic compounds containing a rareearth metal include elements from Atomic No. 57, La, to Atomic No. 71,Lu, in the periodic table.

[0352] In the present invention, the light emitting material means alight emitting substance itself. In the present invention, the lightemitting part is a metal complex or the like, which is bonded to apolymer. That is, a light emitting substance is a polymer-in-itself,which is also a light emitting material. However, for the sake ofexplanation, the light emitting part bonded to a polymer is in somecases referred to as a light emitting substance. In a broader sense, theterm light emitting material is used inclusive of those substances thatconstitute a light emitting layer containing a light emitting substance,a binder, a hole transporting material and an electron transportingmaterial.

[0353] In the present invention, the light emitting part is nonionic.This is because if the light emissive part is ionic, application of avoltage to the light emitting layer containing the light emitting partresults in the occurrence of electrochemical luminescence, which has aresponse speed as slow as an order of minutes, so that it is notsuitable for applications to displays.

[0354] In the present invention, the expression “the light emitting partconstitutes a part of a polymer” means that the structure of a lightemitting part constitutes at least one repeating unit of a polymer. Inthe case where the polymer concerned is a copolymer, that expressionmeans that at least one constituent monomer has the structure of a lightemitting part. The light emitting part may constitute the main chain ofa polymer or a side chain (a pendant group or the like).

[0355] The expression “the light emitting part is bonded to a polymer”means that it is only required that the light emitting part is bonded tothe polymer compound regardless of the degree and form of bonding.Specific method of this bonding may include a method of incorporatingthe light emitting part as a main chain of the polymer, a method ofbonding the light emitting part to the polymer as a side chain(including a pendant group) and the like. However, the present inventionis not limited thereto. In the case of the transition metal complexesand rare earth metal complexes, mention may be made of a method ofincorporating at least one of the ligands that constitute the complexinto the main chain of the polymer, a method of bonding at least one ofligands that constitute the complex into a side chain of the polymer andthe like.

[0356] Examples of the ligand used for the above-mentioned transitionmetal complexes and rare earth metal complexes include acetylacetonato,2,2]-bipyridine, 4,4′-dimethyl-2,2′-bipirydine, 1,10-phenanthroline,2-phenylpyridine, porphyrin, phthalocyanine, pyrimidine, quinoline,2-benzothienylpyridine and/or derivatives thereof. However, the presentinvention is by no means limited thereto. One kind or plural kinds ofligands may be coordinated for a single complex. The above-mentionedcomplex compounds that can be used include a binuclear complex or apolynuclear complex or a double complex form composed of two or morekinds of complexes.

[0357] In the present invention, the metal atom that serves as a centralmetal of the metal complex structure used in the light emitting part isbound to at least one site of a polymer. The method of achieving this isnot particularly limited and includes various formations includingcomplex formation through coordinate bonds, complex formation throughcharge transfer, covalent bonds, ionic bonds, and the like. In thiscase, the method of bonding ligands to a polymer to form a complex of alight emitting substance is preferred since it can immobilize theligands to the polymer with a reduced change in the state of electron ofthe light emitting substance. On this occasion, the method of bindingligands to a polymer to form a complex is particularly preferred sinceit is easy to design and synthesize the material. In the case where themetal atom that serves as the central metal is ion, a method ofrendering the light emitting part neutral is adopted for the reasonsdescribed above. This method includes, for example, a method of formingan organometallic compound having a coordinate bond together with acovalent bond sufficient for neutralizing the valence of the metal ion.However, the present invention is by no means limited thereto.

[0358] The polymer that immobilizes the metal atom in the presentinvention is not particularly limited. For example, polymers havingbound to the main chain or side chain thereof a heterocyclic compoundhaving capability of coordination, such as pyridine group, bipyridylgroup, pyrimidine group, quinoline group, a phenylpyridine group orbenzothienylpyridine group may be used. Specific examples of such apolymer include polymers containing ligands in the main chain and/orderivatives thereof, such as poly(pyridinediyl), poly(bipyridinediyl),poly(quinolinediyl), poly(phenylpyridinediyl) andpoly(benzothienylpyridinediyl), polymers having ligands in the sidechain thereof and/or derivatives thereof, such as poly(vinylpyridine),poly((meth)acrylpyridine), poly(vinylquinoline),poly(vinylphenylpyridine) and poly(vinylbenzothienylpyridine), and/orpolymers having combined the above-mentioned structures, and the like.

[0359] The polymer that can be used in the present invention may be acopolymer of a monomer unit having a light emitting part thatconstitutes a part thereof or is bound thereto and a monomer unit havingno light emitting part. Examples of the monomer unit having no lightemitting part include alkyl (meth) acrylates such as methyl acrylate andmethyl methacrylate, styrene and derivatives thereof. However, thepresent invention is not limited thereto.

[0360] The use of the copolymer containing a monomer unit having nolight emitting part as described above as a light emitting layer of anorganic light emitting device improves the processability of it andprovides flexibility to the film after film formation. This is extremelyadvantageous in fabricating a flexible light emitting device using apolymer film substrate.

[0361] The polymer used in the present invention has a degree ofpolymerization of preferably from 5 to 10,000 and more preferably from10 to 5,000.

[0362] Since the molecular weight of the polymer depends on themolecular weight and degree of polymerization of the constituent monomeror monomers, it is generally difficult to determine a suitable range ofmolecular weight of the polymer used in the present invention. However,usually, the molecular weight of the polymer used in the presentinvention has a weight average molecular weight of preferably from 1,000to 2,000,000 and more preferably from 5,000 to 1,000,000, independentlyof the above-mentioned degree of polymerization.

[0363] Here, the method of measuring molecular weight includes themethods described in “Koubunshi-Kagaku no Kiso (Basis of PolymerChemistry)” (Tokyo Kagaku Dojin, 1978), that is, a GPC method (gelpermeation chromatography), a method using osmotic pressure, a lightscattering method, an ultracentrifugation method and so forth.

[0364] In the organic light emitting device of the present invention,light emission occurs by the following mechanism. That is, electricexcitation generates 25% of the lowest excited singlet state and 75% ofthe lowest excited triplet state. In the case of using a transitionmetal complex or a rare earth metal complex as a light emittingsubstance, the intersystem crossing from the lowest excited singletstate to the lowest excited triplet state tends to occur due to theheavy atom effect, so that the ratio of the lowest excited triplet stateincreases to more than 75%. In the case of the transition metal complex,which emits phosphorescence from the lowest excited triplet state, thereexists nonradiative transition together with radiative transition thatemits phosphorescence. On the other hand, in the case of the rare earthmetal complex, the excitation energy of the lowest excited triplet stateof the ligand is transferred to the central metal ion and light emissionoccurs from the excitation level of the central metal ion. On thisoccasion, too, there exists nonradiative transition together withradiative transition that causes light emission. These nonradiativetransitions cannot be prevented from occurring unless low temperature aslow as the temperature of liquid nitrogen is used. Usually, lightemission of the above-mentioned compounds at room temperature isextremely weak.

[0365] However, in the organic light emitting device of the presentinvention, immobilization of the light emitting substance to the polymeron the level of molecules inhibits the vibration of molecules so thatloss of excited energy in the form of vibration of molecules isprevented. Generally, the excited triplet states are deactivated withoxygen. However, in the organic light emitting device of the presentinvention, confinement of the light emitting substance in the polymermakes it possible to prevent the invasion of oxygen.

[0366] The polymer light emitting material of the present invention canbe prepared by polymerizing a polymerizable composition containing atleast one light emitting compound. The polymerizable composition as usedherein means a composition that contains a polymerizable compound havingat least one polymerizable functional group such as a (meth)acrylicgroup, a vinyl group, a styryl group, an isocyanate group, or athiocyanate group.

[0367] When the number of polymerizable functional groups in thepolymerizable compound is 1, the polymer after the polymerization has nocrosslinked structure. When the number of polymerizable functionalgroups in the polymerizable compound is 2 or more, the polymer after thepolymerization has a crosslinked structure. Since the crosslinkedpolymer is excellent in thermal stability, it is preferable that atleast one of the polymerizable compounds to be used is a crosslinkablecompound having two or more polymerizable functional groups.

[0368] In the present invention, the polymerizable compound in thepolymerizable composition used for the polymer light emitting materialmay be a light emitting compound having a polymerizable functionalgroup, an electron transporting compound having a polymerizablefunctional group, a hole transporting compound having a polymerizablefunctional group, or mixtures of these with other polymerizablecompounds. It is preferred that the light emitting compound used in thepresent invention is a light emitting compound having theabove-mentioned polymerizable functional group. In the case where thepolymerizable composition used for the polymer light emitting materialof the present invention contains a polymerizable compound other thanthe light emitting compound having a polymerizable functional group, thepolymer light emitting material of the present invention serves as acopolymer of the light emitting compound and other polymerizablecompound.

[0369] The light emitting part includes conjugated structures such as astilbene structure, transition metal complexes and the like. From theviewpoints of stability, freedom in design and the like, metal complexstructures are preferred.

[0370] The light emitting layer of the organic light emitting device ofthe present invention, which is a layer containing a light emittingsubstance bound to a polymer as a light emitting material, may containother light emitting material, a hole transporting material, an electrontransporting material and so forth.

[0371] Specifically, in order to further increase the carriertransportability of the phosphorescent emissive polymer compound of thepresent invention, the organic light emitting device of the presentinvention may use a composition containing the polymer compound of thepresent invention and a carrier transporting compound as a lightemitting material.

[0372] That is, a hole transporting compound and an electrontransporting compound may be mixed with the phosphorescent emissivepolymer compound of the present invention. When the phosphorescentemissive polymer compound of the present invention is hole transporting,it is preferred to mix an electron transporting compound therewith. Onthe contrary, when the phosphorescent emissive polymer compound of thepresent invention is an electron transporting, it is preferred to mix ahole transporting compound therewith: On this occasion, the holetransporting and the electron transporting compound may each be a lowmolecular weight compound or a polymer.

[0373] As the low molecular weight hole transporting compound to beblended in the phosphorescent polymer compound of the present invention,known hole transporting materials including triphenylamine derivativessuch as TPD(N,N′-diphenyl-N,N′-(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine), α-NPD(4,4′-bis[N-(1-naphthyl)-N-phenylamino)biphenyl), and m-MTDATA(4,4′,4″-tris(3-methylphenylphenylamino)triphenylamine) and carbazolederivatives such as CBP (4,4′-N,N′-dicarbazole-biphenyl) may be used.However, the present invention is not limited thereto.

[0374] The polymer hole transporting compound to be blended in thephosphorescent emissive polymer compound of the present inventioninclude in addition to poly (N-vinylcarbazole), polymer compoundsobtained by polymerizing monomers composed of the above-mentioned lowmolecular weight hole transporting compound, such as TPD, α-NPD,m-MTDATA, or CPD, to which a polymerizable functional group such as avinyl group, a styryl group, an acrylate group, or a methacrylate grouphas been introduced, polymer compounds having a triphenylamine skeletonas disclosed in Japanese Patent Application Laid-open No. 8-157575 andso forth. However, the present invention is by no means limited thereto.

[0375] On the other hand, as the low molecular weight electrontransporting compound to be blended in the phosphorescent polymercompound of the present invention, quinolinol derivative metal complexessuch as Alq₃ (trisaluminum quinolinol), oxadiazole derivatives such asPBD (2-biphenyl-4-yl-5-(4-tertbutylphenyl)-1,3,4-oxadiazole) and OXD-7(1,3-bis[5-(p-tertbutylphenyl)-1,3,4-oxadiazol-2-yl]benzene, triazolederivatives such as TAZ(3-biphenyl-4-yl-5-(4-tertbutylphenyl)-4-phenyl-4H-1,2,4-triazole),imidazole derivatives, triazine derivatives and so forth may be used.However, the present invention is by no means limited thereto.

[0376] The polymer electron transporting compound to be blended in thephosphorescent polymer compound of the present invention include inaddition to the poly PBD (compound obtained by polymerizing a monomercomposed of the PBD described above having introduced therein a vinylgroup) as disclosed in Japanese Patent Application Laid-open No.10-1665, compounds obtained by polymerizing monomers composed of the lowmolecular weight electron transporting compound such as theabove-mentioned Alq₃, OXD-7, or TAZ to which a polymerizable functionalgroup, such as a vinyl group, a styryl group, an acrylate group or amethacrylate group, has been introduced. However, the present inventionis by no means limited thereto.

[0377] The blending ratio of the low molecular weight hole transportingcompound and/or electron transporting compound to be blended with thephosphorescent emissive polymer compound of the present invention ispreferably from 0 to 100 mass %, more preferably from 10 to 70 mass %,and particularly preferably from 20 to 50 mass % based on thephosphorescent emissive polymer compound of the present invention.Further, the blending ratio of the high molecular weight holetransporting compound and/or electron transporting compound to beblended with the phosphorescent(fluorescent?) emissive compound of thepresent invention is preferably from 0 to 200 mass %, more preferablyfrom 20 to 150 mass %, and particularly preferably from 40 to 100 mass %based on the phosphorescent emissive compound of the present invention.

[0378] For improving the physical properties and the like of the filmobtained by film formation, a composition obtained by blending thephosphorescent emissive polymer compound or composition of the presentinvention with a polymer compound that does not participate in the lightemission characteristics may also be used as a light emitting material.For example, to impart flexibility to the obtained film, PMMA(poly(methyl methacrylate) ), polycarbonate, polystyrene and the likemay be blended. However, the present invention is by no means limitedthereto.

[0379] The blending ratio of the polymer compound that does notparticipate in the light emission characteristics to be blended with thephosphorescent emissive polymer compound of the present invention ispreferably from 0 to 40 mass %, more preferably from 0 to 20 mass % andparticularly preferably from 0 to 10 mass %.

[0380] Specific examples of the polymerizable light emitting compoundused in the present invention include metal complexes having introducedtherein polymerizable functional groups as represented by the followingformulae (C-1), (D-1), (E-1), (F-1) and (G-1), respectively.

[0381] In the formula (C-1), at least one of A^(c), B^(c), and C^(c)represents a substituent having a polymerizable functional group, andthe remainder of A^(c), B^(c), and C^(c) independently represent ahydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonicacid group, a sulfonic acid ester group, or an organic group having 1 to20 carbon atoms which may have one or more heteroatoms. R¹ to R²¹independently represent a hydrogen atom, a halogen atom, a nitro group,an amino group, a sulfonic acid group, a sulfonic acid ester group, oran organic group having 1 to 20 carbon atoms which may have one or moreheteroatoms.

[0382] In the formula (D-1), at least one of X^(1D), Y^(1D), and Z^(1D)represents a substituent having a polymerizable functional group, andthe remainder of X^(1D), Y^(1D), and Z^(1D) independently represent ahydrogen atom, or an organic group having 1 to 20 carbon atoms which mayhave one or more heteroatoms. R¹ to R¹⁶ independently represent ahydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonicacid group, a sulfonic acid ester group, or an organic group having 1 to20 carbon atoms which may have one or more heteroatoms.

[0383] In the formula (E-1), X^(E) represents a substituent having apolymerizable functional group. R^(1E), R^(2E) and R^(3E) independentlyrepresent a hydrogen atom, a halogen atom, or an organic group having 1to 20 carbon atoms which may have one or more heteroatoms. R⁴ to R¹⁹independently represent a hydrogen atom, a halogen atom, a nitro group,an amino group, a sulfonic acid group, a sulfonic acid ester group, oran organic group having 1 to 20 carbon atoms which may have one or moreheteroatoms.

[0384] In the formula (F-1), at least one of X^(1F), Y^(1F), and Z^(1F)represents a substituent having a polymerizable functional group, andthe remainder of X^(1F), Y^(1F), and Z^(1F) independently represent ahydrogen atom, a halogen atom, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms. R¹ to R¹⁶ independentlyrepresent a hydrogen atom, a halogen atom, a nitro group, an aminogroup, a sulfonic acid group, a sulfonic acid ester group, or an organicgroup having 1 to 20 carbon atoms which may have one or moreheteroatoms.

[0385] In the formula (D-1), L represents a monovalent anionic bidentateligand, X^(G) represents a substituent having a polymerizable functionalgroup, and R¹ to R⁷ independently represent a hydrogen atom, a halogenatom, a nitro group, an amino group, a sulfonic acid group, a sulfonicacid ester group, or an organic group having 1 to 20 carbon atoms whichmay have one or more heteroatoms.

[0386] Hereinafter, the polymerizable compounds of the formulae (C-1) to(G-1) will be described in detail.

[0387] Polymerizable Compound (C-1)

[0388] The substituent having a polymerizable functional grouprepresented by A^(C), B^(C) and C^(C) in the formula (C-1) includessubstituents having a vinyl group, an acrylate group, a methacrylategroup, a urethane (meth)acrylate group such as amethacryloyloxyethylcarbamate group, a styryl group and its derivatives,a vinyl amide group and its derivative, respectively. Among thesepolymerizable functional groups, an acrylate group, a methacrylate groupand a urethane (meth)acrylate group are preferred from the viewpoint ofpolymerizability. The position to which these substituents are bondedmay be any one of the 2-, 3-, 4- and 5-positions of the phenyl group ofthe phenylpyridine ligand.

[0389] In the formulae (C-1) to (C-5) and (C-8) to (C-11), theexpression “organic group having 1 to 20 carbon atoms which may have oneor more heteroatoms” is not particularly limited as far as it is notdetrimental to the purpose of the present invention. Preferred examplesof such organic group include an alkyl group, an alkoxy group, analkoxyalkyl group, an aryl group, an aryloxy group, an aralkyl group oran aralkoxy group having 1 to 20 carbon atoms and halogen-substitutedderivatives thereof.

[0390] The substituents having no polymerizable functional grouprepresented by A^(C), B^(C) and C^(C), and R¹ to R²¹ in the formula(C-1) include a hydrogen atom, a halogen atom, a nitro group, an aminogroup, a sulfonic acid group, a sulfonic acid ester group such as methylsulfonate, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl,isobutyl, tert-butyl, amyl, and hexyl, alkoxy groups such as methoxy,ethoxy, propoxy, isobutoxy, and tert-butoxy, an acetoxy group, an estergroup such as propoxycarbonyl, and the like organic groups. Theseorganic groups may contain substituents such as a halogen atom, a nitrogroup, and an amino group.

[0391] Next, examples of the synthesis methods for the polymerizablecompounds of formula (C-1) will be presented below. However, the presentinvention is by no means limited thereto.

[0392] A first synthesis method is a method of producing a polymerizablecompound containing a mononuclear iridium complex part by reacting abinuclear iridium complex represented by the formula (C-8) with aphenylpyridine derivative represented by the formula (C-9) to obtain amononuclear iridium complex having a reactive substituent as anintermediate, and then reacting the reactive substituent of theintermediate with a compound having a polymerizable functional group.

[0393] wherein X^(C) and Y^(C) independently represent a reactivesubstituent, or a hydrogen atom, a halogen atom, a nitro group, an aminogroup, a sulfonic acid group, a sulfonic acid ester group, or an organicgroup having 1 to 20 carbon atoms which may have one or moreheteroatoms, and R¹ to R²⁸ independently represent a hydrogen atom, ahalogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms.

[0394] wherein Z^(C) represents a reactive substituent, or a hydrogenatom, a halogen atom, a nitro group, an amino group, a sulfonic acidgroup, a sulfonic acid ester group, or an organic group having 1 to 20carbon atoms which may have one or more heteroatoms, and R¹ to R⁷independently represent a hydrogen atom, a halogen atom, a nitro group,an amino group, a sulfonic acid group, a sulfonic acid ester group, oran organic group having 1 to 20 carbon atoms which may have one or moreheteroatoms, provided that at least one of X^(C) and Y^(C) in theformula (C-8) and Z^(C) in the formula (C-9) is a reactive substituent.

[0395] The binuclear iridium complex of the formula (C-8) can besynthesized by the known method (S. Lamansky et al., InorganicChemistry, 40, 1704 (2001)). Examples of R¹ to R²⁸ in the formula (C-8)include a hydrogen atom, a halogen atom, a nitro group, an amino group,a sulfonic acid group, a sulfonic acid ester group such as methylsulfonate, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl,isobutyl, tert-butyl, amyl, and hexyl, alkoxy groups such as methoxy,ethoxy, propoxy, isobutoxy, and tert-butoxy, an acetoxy group, an estergroup such as propoxycarbonyl, and the like organic groups. Theseorganic groups may contain substituents such as a halogen atom, a nitrogroup, and an amino group.

[0396] At least one of X^(C) and Y^(C) in the formula (C-8) and Z^(C) inthe formula (C-9) is a reactive substance, for example, a hydroxy group.However, the present invention is by no means limited thereto. Further,the reactive substituent may be protected with a protective group. Inthis case, the reaction is performed by using the complex or compoundhaving a protected reactive substituent as it is to obtain a mononucleariridium complex, which then is subjected to deprotection to obtain amononuclear iridium complex having a reactive substituent as anintermediate. Thereafter, the reactive substituent of the intermediateand a compound having a polymerizable functional group are reacted toobtain a polymerizable compound containing a mononuclear iridium complexpart. From the functional groups for the reactive substituents areexcluded the above-mentioned polymerizable functional groups.

[0397] Examples of R¹ to R⁷ in the compound of the formula (C-9) includea hydrogen atom, a halogen atom, a nitro group, an amino group, asulfonic acid group, a sulfonic acid ester group such as methylsulfonate, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl,isobutyl, tert-butyl, amyl, and hexyl, alkoxy groups such as methoxy,ethoxy, propoxy, isobutoxy, and tert-butoxy, an acetoxy group, an estergroup such as propoxycarbonyl, and the like organic groups. Theseorganic groups may contain substituents such as a halogen atom, a nitrogroup, and an amino group.

[0398] The polymerizable functional group in the compound having apolymerizable functional group to be reacted with the above-mentionedintermediate includes, for example, substituents having a vinyl group,an acrylate group, a methacrylate group, a urethane (meth)acrylate groupsuch as a methacryloyloxyethylcarbamate group, a styryl group and itsderivatives, a vinyl amide group and its derivative, respectively. Amongthese polymerizable functional groups, an acrylate group, a methacrylategroup and a urethane (meth)acrylate group are preferred from theviewpoint of polymerizability.

[0399] In the first synthesis method, when X^(C) and Y^(C) in thebinuclear iridium complex of the formula (C-8) are nonreactivesubstituents and Z^(C) in the phenylpyridine derivative of the formula(C-9) is a reactive substituent, a mononuclear iridium complex having asingle reactive substituent is obtained as an intermediate by thereaction and further reaction of the intermediate with a compound havinga polymerizable functional group can give rise to a monofunctionalpolymerizable compound containing a mononuclear iridium complex part.Further, when X^(C) and Y^(C) in the binuclear iridium complex of theformula (C-8) are reactive substituents and Z^(C) in the phenylpyridinederivative of the formula (C-9) is a nonreactive substituent, amononuclear iridium complex having two reactive substituents is obtainedas an intermediate by these reactions and further reaction of theintermediate with a compound having a polymerizable functional group cangive rise to a bifunctional polymerizable compound containing amononuclear iridium complex part.

[0400] A second synthesis method for the polymerizable compound offormula (C-1) is a method of producing a polymerizable compoundcontaining an iridium complex part having a predetermined number ofpolymerizable functional groups by reacting the iridium complex of theformula (C-10) as an intermediate with a compound having a polymerizablefunctional group in a predetermined molar ratio.

[0401] wherein X^(C) represents a reactive substituent, and R¹ to R²¹independently represent a hydrogen atom, a halogen atom, a nitro group,an amino group, a sulfonic acid group, a sulfonic acid ester group, oran organic group having 1 to 20 carbon atoms which may have one or moreheteroatoms.

[0402] The reactive substituent X^(C) in the iridium complex of theformula (C-10) includes, for example, a hydroxyl group and an aminogroup. However, the present invention is by no means limited thereto. Onthe other hand, the compound having a polymerizable functional group tobe reacted with the iridium complex of the formula (C-10) includes, forexample, a polymerizable acid halide and a polymerizable isocyanate.However, the present invention is by no means limited thereto.

[0403] Next, the use of the second synthetic method in producingpolymerizable acid halides and/or polymerizable isocyanates will bedescribed in detail.

[0404] In the case where the molar ratio of the iridium complex of theformula (C-10) to the polymerizable acid halide and/or polymerizableisocyanate is close to 1:1, for example, 1:(0.5 to 1.5), a mixturecomposed mainly of a monofunctional polymerizable compound can beobtained. Purification of the product affords the monofunctionalpolymerizable compound. On the other hand, in the case where this molarratio is close to 1:2, for example, 1:(1.5 to 2.5), a mixture composedmainly of a bifunctional polymerizable compound can be obtained.Purification of the product affords the bifunctional polymerizablecompound. Further, in the case where the molar ratio is close to 1:3,for example, 1:(2.5 or more), a mixture composed mainly of atrifunctional polymerizable compound can be obtained. Purification ofthe product affords the trifunctional polymerizable compound. However,when the above-mentioned molar ratio is 1:(3 or more), purification forremoving mono- and bifunctional polymerizable compounds is not alwaysnecessary. In the case where mono- and bifunctional polymerizablecompounds are synthesized, a polymerizable acid halide is reacted in apredetermined molar ratio and then a reaction for rendering the residualreactive substituent remaining in the product nonreactive is performed.In the case where the reactive substituent is a hydroxyl group, examplesof the unpolymerizable compound used for this purpose include alkylhalides, carboxylic acids, carboxylic acid halides, sulfonic acidhalides, chloroformates, isocyanates and the like. However, the presentinvention is by no means limited thereto.

[0405] Examples of the polymerizable acid halide used in the secondsynthetic method include acrylic acid chloride, methacrylic acidchloride and the like. Examples of the unpolymerizable acid halideinclude propionic acid chloride, acetic acid chloride and the like.Examples of the polymerizable isocyanate include methacryloylisocyanate, methacryloyloxyethyl isocyanate and the like.Unpolymerizable isocyanate includes, for example, hexyl isocyanate,benzyl isocyanate and the like.

[0406] Still another synthetic method for the polymerizable compound offormula (C-1) includes, for example, a method of producing amonofunctional polymerizable compound containing an iridium complex partby reacting iridium (III) bis(2-phenylpyridinato)acetylacetonato complexwith the phenylpyridine derivative of the formula (C-9) having areactive substituent and then introducing to the product a polymerizablesubstituent.

[0407] The polymer and copolymer of the present invention has a degreeof polymerization of preferably from 3 to 5,000.

[0408] Polymerizable Compound (D-1)

[0409] In the substituent having a polymerizable functional grouprepresented by X^(1D), Y^(1D) and Z^(1D) in the formula (D-1), apolymerizable functional group may be any of a radical polymerizablegroup, a cation polymerizable group, an anion polymerizable group, anaddition polymerizable group, and a condensation polymerizable group.Among these, a radical polymerizable functional group is preferred.Examples of the polymerizable functional group include a vinyl group, anallyl group, an alkenyl group, an acrylate group, a methacrylate group,a urethane (meth)acrylate group such as methacryloyloxyethyl carbamate,a styryl group and derivatives thereof, a vinyl amide group andderivatives thereof. Among the polymerizable functional groups, anacrylate group, a methacrylate group and a urethane (meth)acrylate groupare preferred from the viewpoint of polymerizability.

[0410] In the formulae (D-1), (D-2), (D-14) and (D-17) to (D-23), theexpression “organic group having 1 to carbon atoms which may have one ormore heteroatoms” is not particularly limited as far as it is notdetrimental to the purpose of the present invention. Preferred examplesof such organic group include an alkyl group, an alkoxy group, analkoxyalkyl group, an aryl group, an aryloxy group, an aralkyl group oran aralkoxy group having 1 to 20 carbon atoms and halogen-substitutedderivatives thereof.

[0411] In the formulae (D-1), (D-2), (D-14) and (D-18) to (D-23),examples of the substituents having no polymerizable functional grouprepresented by Q^(1D), Q^(2D) and Q^(3D) out of X^(1D), Y^(1D) andZ^(1D), and Q^(1D) to Q^(3D) include a hydrogen atom, alkyl groups suchas methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl,and hexyl, alkoxy groups such as methoxy, ethoxy, propoxy, isobutoxy,and tert-butoxy, an acetoxy group, an ester group such aspropoxycarbonyl, an aryl group, and the like organic groups.

[0412] In the formulae (D-1), (D-17) and (D-20), examples of R¹ to R¹⁶and R¹⁷ to R³² in each formula include a hydrogen atom, a halogen atom,a nitro group, an amino group, a sulfonic acid group, a sulfonic acidester group such as methyl sulfonate, alkyl groups such as methyl,ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, and hexyl,alkoxy groups such as methoxy, ethoxy, propoxy, isobutoxy, andtert-butoxy, an acetoxy group, an ester group such as propoxycarbonyl,an aryl group, and the like organic groups. These organic groups maycontain substituents such as a halogen atom, a nitro group, and an aminogroup.

[0413] Next, examples of the synthetic method for the polymerizablecompound of formula (D-1) will be described. However, the presentinvention is by no means limited thereto.

[0414] A first synthetic method is a method of producing a polymerizablecompound containing a mononuclear iridium complex part by reacting abinuclear iridium complex represented by the formula (D-17) with acompound having a polymerizable functional group represented by theformula (D-18) below.

[0415] wherein R¹ to R³² independently represent a hydrogen atom, ahalogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms.

[0416] wherein at least one of X^(1D), Y^(1D), and Z^(1D) represents asubstituent having a polymerizable functional group, and the remainderof X^(1D), Y^(1D), and Z^(1D) independently represent a hydrogen atom,or an organic group having 1 to 20 carbon atoms which may have one ormore heteroatoms.

[0417] The binuclear iridium complex of the formula (D-17) can besynthesized by the known method (S. Lamansky et al., InorganicChemistry, 40, 1704 (2001)). Examples of R¹ to R³² in the formula (D-17)include a hydrogen atom, a halogen atom, a nitro group, an amino group,a sulfonic acid group, a sulfonic acid ester group such as methylsulfonate, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl,isobutyl, tert-butyl, amyl, and hexyl, alkoxy groups such as methoxy,ethoxy, propoxy, isobutoxy, and tert-butoxy, an acetoxy group, an estergroup such as propoxycarbonyl, and the like organic groups. Theseorganic groups may contain substituents such as a halogen atom, a nitrogroup, and an amino group.

[0418] At least one of the substituents X^(1D), Y^(1D) and Z^(1D) of thecompound of the formula (D-18) is a substituent having polymerizablefunctional group and means the same group as explained on the formula(D-1). The substituent having no polymerizable functional groups out ofthe substituents represented by the substituents X^(1D), Y^(1D) andZ^(1D) of the compound of the formula (D-18) are the same as the formula(D-1).

[0419] A second synthesis method for the polymerizable compound offormula (D-1) is a method of producing a polymerizable compoundcontaining a mononuclear iridium complex part by reacting a binucleariridium complex represented by the formula (D-17) with a compound havinga reactive substituent represented by the formula (D-19) below to obtaina mononuclear iridium complex having a reactive substituent as anintermediate, and then reacting the reactive substituent of the obtainedmononuclear iridium complex with a compound having a polymerizablefunctional group.

[0420] wherein R¹ to R³² independently represent a hydrogen atom, ahalogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms.

[0421] wherein at least one of X^(2D), Y^(2D), and Z^(2D) represents areactive substituent, and the remainder of X^(2D), Y^(2D), and Z^(2D)independently represent a hydrogen atom, or an organic group having 1 to20 carbon atoms which may have one or more heteroatoms.

[0422] At least one of the substituents X^(2D), Y^(2D) and Z^(2D) of thecompound of the formula (D-19) is a reactive substituent having afunctional group, for example, a hydroxyl group. Examples of thefunctional group may include a hydroxyl group, an amino group and acarboxyl group. However, the present invention is by no means limitedthereto. The reactive substituent having a functional group includes ahydroxyl group, a hydroxyalkyl group, a hydroxyphenyl group and thelike.

[0423] Further, the reactive substituent may be protected with aprotective group. In this case, the reaction is performed by using thecomplex or compound having a protected reactive substituent, as it is toobtain a mononuclear iridium complex, which then is subjected todeprotection to obtain a mononuclear iridium complex having a reactivesubstituent as an intermediate. Thereafter, the reactive substituent ofthe intermediate and a compound having a polymerizable functional groupare reacted to obtain a polymerizable compound containing a mononucleariridium complex part. From the functional groups for the reactivesubstituents are excluded the above-mentioned polymerizable functionalgroups.

[0424] Examples of the substituents having no polymerizable functionalgroup represented by X^(2D), Y^(2D) and Z^(2D) in the formula (D-19)include a hydrogen atom, a halogen atom, alkyl groups such as methyl,ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, and hexyl,alkoxy groups such as methoxy, ethoxy, propoxy, isobutoxy, andtert-butoxy, an acetoxy group, an ester group such as propoxycarbonyl,an aryl group, and the like organic groups. These organic groups mayhave a substituent such as a halogen atom.

[0425] The compound having a polymerizable functional group to bereacted with the mononuclear iridium complex having a reactivesubstituent obtained by the reaction between the binuclear iridiumcomplex and the compound of the formula (D-19) having a reactivesubstituent must have in addition to the polymerizable group afunctional group having a group reactive with the reactive substituentsX^(2D), Y^(2D) and Y^(3D) in the formula (D-19). In the case of thesecond synthesis method for the polymerizable compounds according to thepresent invention, R¹ to R³² in the formula (D-17) must be selected soas to be groups that do not react with the compound having apolymerizable functional group to be reacted with the above-mentionedmononuclear iridium complex.

[0426] Examples of the compound having a polymerizable functional groupto be reacted with the above-mentioned mononuclear iridium complexinclude polymerizable acid chlorides and polymerizable isocyanates.However, the present invention is by no means limited thereto. Thepolymerizable functional group may be any of a radical polymerizablegroup, a cation polymerizable group, an anion polymerizable group, anaddition polymerizable group, and a condensation polymerizable group.Among these, a radical polymerizable functional group is preferred.Examples of the polymerizable functional group include a vinyl group, anallyl group, an alkenyl group, an acrylate group, a methacrylate group,a urethane (meth)acrylate group such as methacryloyloxyethyl carbamate,a styryl group and derivatives thereof, a vinyl amide group andderivatives thereof. Among the polymerizable functional groups, anacrylate group, a methacrylate group and a urethane (meth)acrylate groupare preferred from the viewpoint of polymerizability. Specifically,examples of the polymerizable acid chloride include acrylic acidchloride, methacrylic acid chloride and the like. Examples of thepolymerizable isocyanate include methacryloyl isocyanate andmethacryloyloxyethyl isocyanate and the like.

[0427] The chemical formulae such as the formula (D-1) representing thecompounds of the present invention represent metal complex structures,in which O—C—C—C—O indicates resonant structures. Of course they includechemically acceptable structures.

[0428] Polymerizable Compound (E-1)

[0429] The substituent having a polymerizable functional grouprepresented by X^(E) in the formula (E-1) is preferably a substituenthaving a carbon-carbon double bond as a polymerizable functional group,examples of which include substituents having a vinyl group, anacryloyloxy group, a methacryloyloxy group, a urethane (meth)acryloyloxygroup, such as a methacryloyloxyethyl-carbamate group, a styryl groupand its derivatives, and a vinyl amide group and its derivative,respectively. Among these polymerizable functional groups, anacryloyloxy group, a methacryloyloxy group, a urethane (meth)acryloyloxygroup, and a styryl group are preferred from the viewpoint ofpolymerizability. The position to which these substituents are bondedmay be any one of the 3-, 4-, 5- and 6-positions of the picolinic acidligand.

[0430] In the formulae (E-1), and (E-9) to (E-12), the expression“organic group having 1 to 20 carbon atoms which may have one or moreheteroatoms” is not particularly limited as far as it is not detrimentalto the purpose of the present invention. Preferred examples of suchorganic group include an alkyl group, an alkoxy group, an alkoxyalkylgroup, an aryl group, an aryloxy group, an aralkyl group or an aralkoxygroup having 1 to 20 carbon atoms and halogen-substituted derivativesthereof.

[0431] Examples of R^(1E), R^(2E) and R^(3E) in the formulae (E-1)include a hydrogen atom, a halogen atom, alkyl groups such as methyl,ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, and hexyl,alkoxy groups such as methoxy, ethoxy, propoxy, isobutoxy, andtert-butoxy, an aralkyl group, an acetoxy group, an ester group such aspropoxycarbonyl, and the like organic groups. These substituents mayfurther have a substituent such as a halogen atom.

[0432] Examples of R⁴ to R¹⁹ in the formula (E-1) include a hydrogenatom, a halogen atom, a nitro group, an amino group, a sulfonic acidgroup, a sulfonic acid ester group such as methyl sulfonate, alkylgroups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl,tert-butyl, amyl, and hexyl, alkoxy groups such as methoxy, ethoxy,propoxy, isobutoxy, and tert-butoxy, an aralkyl group, an acetoxy group,an ester group such as propoxycarbonyl, and the like organic groups.These organic groups may further have substituents such as a halogenatom, a nitro group, and an amino group. Among these, a hydrogen atom, ahalogen atom and alkyl groups having 1 to 20 carbon atoms are preferred.

[0433] Next, examples of the synthesis methods for the polymerizablecompound of the formula (E-1) will be presented below. However, thepresent invention is by no means limited thereto.

[0434] A first synthesis method for the polymerizable compound of theformula (E-1) is a method of producing a polymerizable compoundcontaining a mononuclear iridium complex part by reacting a binucleariridium complex represented by the formula (E-9) with a picolinic acidderivative represented by the formula (E-10) to obtain a mononucleariridium complex having a reactive substituent as an intermediate, andthen reacting the reactive substituent of the intermediate with acompound having a polymerizable functional group.

[0435] wherein R⁴ to R¹⁹ independently represent a hydrogen atom, ahalogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms.

[0436] wherein Y^(E) represents a reactive substituent. R^(1E), R^(2E)and R^(3E) independently represent a hydrogen atom, a halogen atom, oran organic group having 1 to 20 carbon atoms which may have one or moreheteroatoms.

[0437] The binuclear iridium complex of the formula (E-9) can besynthesized by the known method (S. Lamansky et al., InorganicChemistry, 40, 1704 (2001)). Examples of R⁴ to R¹⁹ in the formula (E-9)include a hydrogen atom, a halogen atom, a nitro group, an amino group,a sulfonic acid group, a sulfonic acid ester group such as methylsulfonate, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl,isobutyl, tert-butyl, amyl, and hexyl, alkoxy groups such as methoxy,ethoxy, propoxy, isobutoxy, and tert-butoxy, an aralkyl group, anacetoxy group, an ester group such as propoxycarbonyl, and the likeorganic groups. These organic groups may contain substituents such as ahalogen atom, a nitro group, and an amino group. Among these, a hydrogenatom, a halogen atom and alkyl groups having 1 to 20 carbon atoms arepreferred.

[0438] The Y^(E) in the formula (E-10) is a reactive substituent,examples of which include groups having an active hydrogen such as ahydroxymethyl group, a hydroxyl group, a mercapto group and an aminogroup, respectively, and a carboxyl group. However, the presentinvention is by no means limited thereto. Further, the reactivesubstituent maybe protected with a protective group. In this case, thereaction is performed as it is, i.e., in a state where the reactivesubstituent is protected with a protecting group to obtain a mononucleariridium complex, which then is subjected to deprotection to obtain amononuclear iridium complex having a reactive substituent as anintermediate. Thereafter, the reactive substituent of the intermediateand a compound having a polymerizable functional group are reacted toobtain a polymerizable compound containing a mononuclear iridium complexpart. From the functional groups for the reactive substituents are to beexcluded the above-mentioned polymerizable functional groups.

[0439] Examples of R^(1E), R^(2E) and R^(3E) in the formula (E-10)include a hydrogen atom, a halogen atom, alkyl groups such as methyl,ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, and hexyl,alkoxy groups such as methoxy, ethoxy, propoxy, isobutoxy, andtert-butoxy, an aralkyl group, an acetoxy group, an ester group such aspropoxycarbonyl, and the like organic groups. These organic groups mayfurther contain substituents such as a halogen atom. Among these, ahydrogen atom, a halogen atom and alkyl groups having 1 to 20 carbonatoms are preferred.

[0440] The compound having a polymerizable functional group to bereacted with the mononuclear iridium complex having a reactivesubstituent (intermediate) obtained by the reaction between thebinuclear iridium complex of the formula (E-9) and the compound of theformula (E-10) having a reactive substituent must have in addition tothe polymerizable group a functional group having a group reactive withthe reactive substituent Y^(E) in the formula (E-10). Examples of such afunctional group include an isocyanato group and a carboxyl group whenthe reactive substituent Y^(E) is a hydroxymethyl group or a hydroxylgroup, or an isocyanato group and an acid chloride (R—COCl) group whenthe reactive substituent Y^(E) is a mercapto group or an amino group. Onthe other hand, R⁴ to R¹⁹ in the formula (E-9) must be selected fromgroups that do not react with the compound having a polymerizablefunctional group to be reacted with the above-mentioned mononucleariridium complex.

[0441] The polymerizable functional group in the compound having apolymerizable functional group to be reacted with the above-mentionedintermediate is preferably a group having a carbon-carbon double bond asa polymerizable functional group, examples of which include a vinylgroup, an acryloyloxy group, a methacryloyloxy group, a urethane(meth)acryloyloxy group, such as a methacryloyloxyethylcarbamate group,a styryl group and its derivatives, a vinyl amide group and itsderivative, respectively. Among these polymerizable functional groups,an acryloyloxy group, a methacryloyloxy group, a urethane(meth)acryloyloxy group, and a styryl group are preferred from theviewpoint of polymerizability.

[0442] The second synthesis method for the polymerizable compound of theformula (E-1) is a method of directly producing a polymerizable compoundcontaining a mononuclear iridium complex part by reacting a binucleariridium complex of the formula (E-9) with a picolinic acid derivative ofthe formula (E-11):

[0443] wherein X^(E) represents a substituent having a polymerizablefunctional group, and R^(1E), R^(2E) and R^(3E) independently representa hydrogen atom, a halogen atom, a nitro group, an amino group, asulfonic acid group, a sulfonic acid ester group, or an organic grouphaving 1 to 20 carbon atoms which may have one or more heteroatoms.

[0444] The X^(E) in the formula (E-11), which is a substituent having apolymerizable functional group, is preferably a substituent having acarbon-carbon double bond as a polymerizable functional group. Examplesthereof include a methacryloyloxy group, amethacryloyloxyethylcarbamoyloxy group, amethacryloyloxy-ethylcarbamoyloxymethyl group, a vinylbenzyloxy group, amethacryloyloxyethyloxycarbonyl group and the like. However, the presentinvention is by no means limited thereto.

[0445] Examples of R^(1E), R^(2E) and R^(3E) in the formula (E-11)include a hydrogen atom, a halogen atom, alkyl groups such as methyl,ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, and hexyl,alkoxy groups such as methoxy, ethoxy, propoxy, isobutoxy, andtert-butoxy, an aralkyl group, an acetoxy group, an ester group such aspropoxycarbonyl, and the like organic groups. These organic groups mayfurther contain substituents such as a halogen atom.

[0446] Polymerizable Compound (F-1)

[0447] In the substituent having a polymerizable functional grouprepresented by X^(1F), Y^(1E) and Z^(1F) in the formula (F-1), apolymerizable functional group may be any of a radical polymerizablegroup, a cation polymerizable group, an anion polymerizable group, anaddition polymerizable group, and a condensation polymerizable group.Among these, a radical polymerizable functional group is preferred.Examples of the polymerizable functional group include those groupshaving a vinyl group, an allyl group, an alkenyl group, an alkenoyloxygroup such as an acryloyloxy group and a methacryloyloxy group, aurethane (meth)acryloyloxy group such as a methacryloyloxyethylcarbamategroup, a styryl group and its derivatives, a vinyl amide group and itsderivatives, respectively. Among these polymerizable functional groups,an acryloyloxy group, a methacryloyloxy group, a urethane(meth)acryloyloxy group, and a styryl group are preferred from theviewpoint of polymerizability.

[0448] In the formulae (F-1), (F-2), (F-12), and (F-15) to (F-21), the“organic group having 1 to 20 carbon atoms which may have one or moreheteroatoms” is not particularly limited as far as it is not detrimentalto the purpose of the present invention and may have a heteroatom suchas an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom.Preferred examples of such an organic group include an alkyl group, analkoxy group, an alkoxyalkyl group, an aryl group, an aryloxy group, anaralkyl group or an aralkoxy group having 1 to 20 carbon atoms andhalogen-substituted derivatives thereof.

[0449] Examples of the substituents having no polymerizable functionalgroup represented by Q^(1F), Q^(2F) and Q^(3F) out of X^(1F), Y^(1F) andZ^(1F) in the formulae (F-1), (F-2), (F-12), and (F-15) to (F-21),include a hydrogen atom, a halogen atom, alkyl groups such as methyl,ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, and hexyl,an aralkyl group, alkoxy groups such as methoxy, ethoxy, propoxy,isobutoxy, and tert-butoxy, an acetoxy group, an ester group such aspropoxycarbonyl, an aryl group, and the like organic groups. Amongthese, a hydrogen atom, a halogen atom, and alkyl groups having 1 to 20carbon atoms are preferred.

[0450] The R¹ to R¹⁶ in the formulae (F-1), (F-15) and (F-18) include ahydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonicacid group, a sulfonic acid ester group such as methyl sulfonate, alkylgroups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl,tert-butyl, amyl, and hexyl, an aralkyl group, alkoxy groups such asmethoxy, ethoxy, propoxy, isobutoxy, and tert-butoxy, an acetoxy group,an ester group such as propoxycarbonyl, an aryl group, and the likeorganic groups, provided that they fall in the range as defined above.These organic groups may further have substituents such as a halogenatom, a nitro group, and an amino group. Among these, a hydrogen atom, ahalogen atom, and alkyl groups having 1 to 20 carbon atoms arepreferred.

[0451] “A”s in the formula (F-6) and (F-9) are organic groups having 3to 20 carbon atoms, containing an acryloyl group, a methacryloyl group,an acryloyloxy group or a methacryloyloxy group. The organic groups mayhave a heteroatom such as an oxygen atom, a nitrogen atom, a sulfuratom, or a halogen atom as far as it is not detrimental to the purposeof the present invention. Preferred examples of such an organic groupinclude an alkyl group, an aryl group and an aralkyl group. Further,these groups may contain an isocyanate bond.

[0452] Next, examples of the synthesis methods for the polymerizablecompound in the formula (F-1) will be presented below. However, thepresent invention is by no means limited thereto.

[0453] A first synthesis method is a method of producing a polymerizablecompound containing a mononuclear iridium complex part by reacting abinuclear iridium complex represented by the formula (F-15) with acompound having a polymerizable functional group represented by theformula (F-16):

[0454] wherein R¹ to R¹⁶ independently represent a hydrogen atom, ahalogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms.

[0455] wherein at least one of X^(1F), Y^(1F), and Z^(1F) represents asubstituent having a polymerizable functional group, and the remainderof X^(1F), Y^(1F), and Z^(1F) independently represent a hydrogen atom, ahalogen atom or an organic group having 1 to 20 carbon atoms which mayhave one or more heteroatoms.

[0456] The binuclear iridium complex of the formula (F-15) can besynthesized by the known method (S. Lamansky et al., InorganicChemistry, 40, 1704 (2001)). Examples of R¹ to R¹⁶ in the formula (F-15)include a hydrogen atom, a halogen atom, a nitro group, an amino group,a sulfonic acid group, a sulfonic acid ester group such as methylsulfonate, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl,isobutyl, tert-butyl, amyl, and hexyl, an aralkyl group such as a benzylgroup, alkoxy groups such as methoxy, ethoxy, propoxy, isobutoxy, andtert-butoxy, an acetoxy group, an ester group such as propoxycarbonyl,and the like organic groups. These organic groups may further containsubstituents such as a halogen atom, a nitro group, and an amino group.Among these, a hydrogen atom, a halogen atom, and alkyl groups having 1to 20 carbon atoms are preferred.

[0457] At least one of the substituents X^(1F), Y^(1F) and Z^(1F) of thecompound of the formula (F-16) is a substituent having polymerizablefunctional group and has the same meaning as explained on the formula(F-1). The substituent having no polymerizable functional grouprepresented by the substituents X^(1E), Y^(1F) and Z^(1F) of thecompound of the formula (F-16) are the same as in the case of theformula (F-1).

[0458] A second synthesis method for the polymerizable compound offormula (F-1) is a method of producing a polymerizable compoundcontaining a mononuclear iridium complex part by reacting a binucleariridium complex represented by the formula (F-15) with a compound havinga reactive substituent represented by the formula (F-17) to obtain amononuclear iridium complex having a reactive substituent as anintermediate, and then reacting the reactive substituent of theintermediate with a compound having a polymerizable functional group:

[0459] wherein R¹ to R¹⁶ independently represent a hydrogen atom, ahalogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms.

[0460] wherein at least one of X^(2F), Y^(2F), and Z^(2F) represents areactive substituent, and the remainder of X^(2F), Y^(2F), and Z^(2F)independently represent a hydrogen atom, a halogen atom or an organicgroup having 1 to 20 carbon atoms which may have one or moreheteroatoms.

[0461] At least one of the substituents X^(2F), Y^(2F) and Z^(2F) of theformula (F-17) is a reactive substituent having a functional group, forexample, a hydroxyl group. Examples of the functional group may includean active hydrogen, such as a hydroxyl group, a mercapto group, and anamino group, and a carboxyl group. However, the present invention is byno means limited thereto. Examples of the reactive substituent having afunctional group include a hydroxyl group, a hydroxyalkyl group, ahydroxyphenyl group, a mercapto group, an amino group and the like.

[0462] Further, the reactive substituent may be protected with aprotective group. In this case, the reaction is performed as it is,i.e., in a state where the reactive substituent is protected with aprotective group to obtain a mononuclear iridium complex, which then issubjected to deprotection to obtain a mononuclear iridium complex havinga reactive substituent as an intermediate. Thereafter, the reactivesubstituent of the intermediate and a compound having a polymerizablefunctional group are reacted to obtain a polymerizable compoundcontaining a mononuclear iridium complex part. From the functionalgroups for the reactive substituents are to be excluded theabove-mentioned polymerizable functional groups.

[0463] The substituents out of the substituents X^(2F), Y^(2F) andZ^(2F) of the compound of the formula (F-19) other than the reactivesubstituents include a hydrogen atom, a halogen atom, alkyl groups suchas methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl,and hexyl, alkoxy groups such as methoxy, ethoxy, propoxy, isobutoxy,and tert-butoxy, an acetoxy group, an ester group such aspropoxycarbonyl, an aryl group, and the like organic groups. Thesesubstituents may further have a substituent such as a halogen atom.

[0464] The compound having a polymerizable functional group to bereacted with the mononuclear iridium complex having a reactivesubstituent obtained by the reaction between the binuclear iridiumcomplex and the compound of the formula (F-17) having a reactivesubstituent must have in addition to the polymerizable group afunctional group having a group reactive with the reactive substituentX^(2F), Y^(2F), and Z^(2F) in the formula (F-17). Examples of such afunctional group include an isocyanato group and a carboxyl group whenthe reactive substituents X^(2F), Y^(2F) or Z^(2F) are groups thatcontain a hydroxyl group, such as a hydroxymethyl group or a hydroxylgroup, or an isocyanato group and an acid chloride (R—COCl) group whenthe reactive substituents X^(2F), Y^(2F) or Z^(2F) are groups thatcontain a mercapto group or an amino group, or a hydroxyl group when thereactive substituents X^(2F), Y^(2F) or Z^(2F) are groups that contain acarboxyl group.

[0465] In the case of the second synthesis method for the polymerizablecompound of formula (F-1), R¹ to R¹⁶ in the formula (F-15) must beselected from groups that do not react with the compound having apolymerizable functional group to be reacted with the above-mentionedmononuclear iridium complex.

[0466] Examples of the compound having a polymerizable functional groupto be reacted with the above-mentioned mononuclear iridium complexinclude polymerizable acid chlorides and polymerizable isocyanates.However, the present invention is by no means limited thereto. In thesecompounds, the polymerizable functional group may be any of a radicalpolymerizable group, a cation polymerizable group, an anionpolymerizable group, an addition polymerizable group, and a condensationpolymerizable group. Among these, a radical polymerizable functionalgroup is preferred. The polymerizable functional group is preferably agroup having a carbon-carbon double bond. Examples thereof include avinyl group, an allyl group, an alkenyl group, an alkenoyloxy group suchas an acryloyloxy group and a methacryloyloxy group, a urethane(meth)acryloyloxy group such as a methacryloyloxyethylcarbamate group, astyryl group and its derivatives, a vinyl amide group and derivativesthereof. Among these polymerizable functional groups, an acryloyloxygroup, a methacryloyloxy group, and a urethane (meth)acryloyloxy groupare preferred from the viewpoint of polymerizability. Specifically,examples of the polymerizable acid chloride include acrylic acidchloride, methacrylic acid chloride and the like. Examples of thepolymerizable isocyanate include methacryloyl isocyanate,methacryloyloxyethyl isocyanate and the like.

[0467] The chemical formulae such as the formula (F-1) representing thecompounds of the present invention represent metal complex structures,in which O—C—C—C—O indicates a resonant structure. Of course theyinclude chemically acceptable structures.

[0468] Polymerizable Compound (G-1)

[0469] The monovalent anionic bidentate ligand represented by L in theformula (G-1) is a monovalent anion compound obtainable by eliminatingone hydrogen atom from a compound having in the molecule a nonioniccoordination site such as a pyridine ring, a carbonyl group, or an iminegroup, and a site that can become a monovalent anionic coordination siteupon elimination of one hydrogen ion, such as a phenyl group, a hydroxylgroup, or a carboxyl group, or from a compound having a conjugatestructure having two coordination sites that can become a monovalentanionic group as a whole upon elimination of one hydrogen ion, such as aβ-diketone. Among these compounds, preferred are compounds that can forma 5-membered or 6-membered ring structure including the iridium atomwhen the compound is coordinated to one iridium atom at the twocoordination sites thereof. Examples of such preferred compounds includemonovalent anionic compounds derived from 2-phenylpyridine, β-diketone,picolinic acid, N-alkylsalicylimine, 8-hydroxyquinoline, and derivativesthereof by eliminating one hydrogen ion. Among these bidentate ligands,monovalent anionic compounds derived from β-diketone, picolinic acid andN-alkylsalicylimine by elimination of one hydrogen atom are preferredfrom the viewpoint of light emission characteristics.

[0470] In the substituent having a polymerizable functional grouprepresented by X^(G) in the formula (G-1), the polymerizable functionalgroup may be any one of a radical polymerizable substituent, a cationpolymerizable substituent, an anion polymerizable substituent, anaddition polymerizable substituent, and a condensation polymerizablesubstituent. Among these, a radical polymerizable functional group ispreferred. The polymerizable functional group is preferably a grouphaving a carbon-carbon double bond. Examples thereof include a vinylgroup, an allyl group, an alkenyl group, alkenoyloxy groups such as anacryloyloxy group and a methacryloyloxy group, a urethane(meth)acryloyloxy group such as methacryloyloxyethyl carbamate, a styrylgroup and derivatives thereof, a vinyl amide group and derivativesthereof. Among the polymerizable functional groups, an acryloyloxygroup, a methacryloyloxy group, a urethane (meth)acrylate and a styrylgroup are preferred from the viewpoint of polymerizability.Specifically, examples of the substituent having a polymerizablefunctional group include a methacryloyloxy group, amethacryloyloxyethylcarbamoyloxy group, and a vinylbenzyloxy group.However, the present invention is by no means limited thereto. Theposition to which these substituents are bonded may be any one of the3-, 4-, 5- and 6-positions of the phenyl group of the phenylpyridineligand.

[0471] In the formulae (G-1), (G-2), (G-6), (G-7), (G-9) and (G-10), the“organic group having 1 to 20 carbon atoms which may have one or moreheteroatoms” in each formula is not particularly limited as far as it isnot detrimental to the purpose of the present invention. Preferredexamples of such organic group include an alkyl group, an alkoxy group,an alkoxyalkyl group, an aryl group, an aryloxy group, an aralkyl group,an aralkoxy group having 1 to 20 carbon atoms and halogen-substitutedderivatives thereof.

[0472] Examples of the R¹ to R⁷ in the formula (G-1) include a hydrogenatom, a halogen atom, a nitro group, an amino group, a sulfonic acidgroup, a sulfonic acid ester group such as methyl sulfonate, alkylgroups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl,tert-butyl, amyl, and hexyl, alkoxy groups such as methoxy, ethoxy,propoxy, isobutoxy, and tert-butoxy, an aralkyl group, an acetoxy group,an ester group such as propoxycarbonyl, and the like organic groups.These organic groups may further have substituents such as a halogenatom, a nitro group, and an amino group. Among these, a hydrogen atom, ahalogen atom and alkyl groups having 1 to 20 carbon atoms are preferred.It should be noted that although in the formula (G-1), the two sets ofR¹ to R⁷ bonded to two phenylpyridine groups are explained to be thesame, they may be different for different phenylpyridine skeletons.

[0473] Among the compounds of the formula (G-1), those compounds inwhich the monovalent anionic bidentate ligand represented by L is acompound derived from β-diketone by elimination of one hydrogen ion isindicated by the formula (G-2).

[0474] wherein A^(1G), A^(2G), and A^(3G) independently represent ahydrogen atom, a halogen atom or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms. X^(G) represents asubstituent having a polymerizable functional group, and R¹ to R⁷independently represent a hydrogen atom, a halogen atom, a nitro group,an amino group, a sulfonic acid group, a sulfonic acid ester group, oran organic group having 1 to 20 carbon atoms which may have one or moreheteroatoms.

[0475] Examples of the A^(1G), A^(2G), and A^(3G) in the formula (G-2)include a hydrogen atom, a halogen atom, alkyl groups such as methyl,ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, and hexyl,alkoxy groups such as methoxy, ethoxy, propoxy, isobutoxy, andtert-butoxy, an aralkyl group, an acetoxy group, an ester group such aspropoxycarbonyl, and the like organic groups. These organic groups mayfurther have substituents such as a halogen atom.

[0476] In the formula (G-2), the substituent having a polymerizablefunctional group, represented by X^(G) and R¹ to R⁷ have the samemeanings as those in the formula (G-1).

[0477] The chemical formulae such as the formula (G-1) representing thecompounds of the present invention represent metal complex structures,and O—C—C—C—O in the chemical formulae such as the formula (G-2)indicates a resonant structure. Of course they include chemicallyacceptable structures.

[0478] Next, examples of the synthesis methods for the polymerizablecompound of formula (G-1) will be presented below. However, the presentinvention is by no means limited thereto.

[0479] A first synthesis method for the polymerizable compounds is amethod of producing a polymerizable compound containing a mononucleariridium complex part by reacting a binuclear iridium complex having areactive substituent represented by the formula. (G-6) with a compoundthat can become a monovalent anionic bidentate ligand upon eliminationof one hydrogen ion to form a mononuclear iridium complex having areactive substituent as an intermediate, and then reacting the reactivesubstituent of the intermediate with a compound having a polymerizablefunctional group:

[0480] wherein Y^(G) is a substituent having a reactive functionalgroup, and R¹ to R⁷ independently represent a hydrogen atom, a halogenatom, a nitro group, an amino group, a sulfonic acid group, a sulfonicacid ester group, or an organic group having 1 to 20 carbon atoms whichmay have one or more heteroatoms.

[0481] The binuclear iridium complex of the formula (G-6) can besynthesized by the known method (S. Lamansky et al., InorganicChemistry, 40, 1704 (2001)).

[0482] The Y^(G) in the formula (G-6) is a substituent having a reactivefunctional group, examples of which include a hydroxyl group, a mercaptogroup, an amino group, and a carboxyl group. However, the presentinvention is by no means limited thereto. The substituent Y^(G) having areactive functional group may be the above-mentioned functional group byitself or a substituent having a functional group such as ahydroxymethyl group. The reactive functional group of Y^(G) may beprotected with a protective group. In this case, the reaction isperformed by using the complex or compound having a protected reactivesubstituent as it is to obtain a mononuclear iridium complex having amonovalent anionic bidentate ligand L, which then is subjected todeprotection to obtain a mononuclear iridium complex having asubstituent Y^(G) containing a reactive functional group as anintermediate. A further reaction between the reactive substituent of theintermediate and a compound having a polymerizable functional groupgives rise to a polymerizable compound containing a mononuclear iridiumcomplex part. From the functional groups for the reactive substituentsare to be excluded the above-mentioned polymerizable functional groups.

[0483] In the formula (G-6), R¹ to R⁷ have the same meanings as those inthe formula (G-1). As in the formula (G-1), the four sets of R¹ to R⁷bonded to four phenylpyridine skeletons may be different for differentphenylpyridine skeletons.

[0484] Examples of the compound that can become a monovalent anionicbidentate ligand upon elimination of one hydrogen ion include2-phenylpyridine, β-diketone, picolinic acid, N-alkylsalicylimine,8-hydroxyquinoline, and derivatives thereof. However, the presentinvention is by no means limited thereto.

[0485] The compound having a polymerizable functional group to bereacted with the mononuclear iridium complex having a substituent Y^(G)containing a reactive functional group obtained by the reaction betweenthe binuclear iridium complex having a substituent containing a reactivefunctional group of the formula (G-6) and the compound that can become amonovalent anionic bidentate ligand upon elimination of one hydrogen ionmust have in addition to the polymerizable group a functional group tobe reacted with a substituent Y^(G) having a reactive functional groupin the formula (G-6). The R¹ to R⁷ in the formula (G-6) must be selectedfrom groups that do not react with the compound having a polymerizablefunctional group to be reacted with the above-mentioned mononucleariridium complex.

[0486] Examples of the compound having a polymerizable functional groupto be reacted with the above-mentioned intermediate includepolymerizable acid chlorides, polymerizable alkyl halides, andpolymerizable isocyanates. However, the present invention is by no meanslimited thereto. The polymerizable functional group may be any one of aradical polymerizable group, a cation polymerizable group, an anionpolymerizable group, an addition polymerizable group, and a condensationpolymerizable group. Among these, a radical polymerizable functionalgroup is preferred. The polymerizable functional group is preferably agroup having a carbon-carbon double bond. Examples thereof include avinyl group, an allyl group, an alkenyl group, alkenoyloxy groups suchas an acryloyloxy group and a methacryloyloxy group, a urethane(meth)acryloyloxy group such as methacryloyloxyethyl carbamate, a styrylgroup and derivatives thereof, a vinyl amide group and derivativesthereof. Among the polymerizable functional groups, an acryloyloxygroup, a methacryloyloxy group, a urethane (meth)acryloyloxy group, anda styryl group are preferred from the viewpoint of polymerizability.Specifically, examples of the polymerizable acid chloride includeacrylic acid chloride, methacrylic acid chloride and the like. Examplesof the polymerizable alkyl halide include vinylbenzyl chloride. Examplesof the polymerizable isocyanate include methacryloyl isocyanate andmethacryloyloxyethyl isocyanate.

[0487] A second synthesis method for the polymerizable compound of theformula (G-1) is a method of directly producing a polymerizable compoundcontaining a mononuclear iridium complex part by reacting a binucleariridium complex represented by the formula (G-7) having a polymerizablefunctional group with a compound that can become a monovalent anionicbidentate ligand upon elimination of one hydrogen ion:

[0488] wherein X^(G) is a substituent having a polymerizable functionalgroup, and R¹ to R⁷ independently represent a hydrogen atom, a halogenatom, a nitro group, an amino group, a sulfonic acid group, a sulfonicacid ester group, or an organic group having 1 to 20 carbon atoms whichmay have one or more heteroatoms.

[0489] In the formula (G-7), the substituent having a polymerizablefunctional group represented by X^(G) has the same meaning as in theformula (G-1). R¹ to R⁷ have the same meanings as those in the formula(G-1).

[0490] Examples of the compound that can become a monovalent anionicbidentate ligand upon elimination of one hydrogen ion include2-phenylpyridine, β-diketone, picolinic acid, N-alkylsalicylimine,8-hydroxyquinoline, and derivatives thereof. However, the presentinvention is by no means limited thereto.

[0491] The composition containing a polymerizable light emittingcompound for use in the polymer light emitting material of the presentinvention may contain an electron transporting compound for forming anelectron transport layer. As the electron transporting compound, knownelectron transporting material, such as quinolinol derivative metalcomplexes, oxadiazole derivatives, and triazole derivatives may be used.However, the present invention is by no means limited thereto. Theelectron transporting materials may be used singly or in admixture withother electron transporting materials.

[0492] The electron transporting compound contained in the compositioncontaining a polymerizable light emitting compound used for the polymerlight emitting material of the present invention may be a electrontransporting material that is polymerizable. The use of electrontransporting compound being polymerizable is more preferable, since thefreedom in selecting the composition containing a polymerizable lightemitting compound for use in the polymer light emitting material of thepresent invention is increased.

[0493] Examples of the polymerizable electron transporting compoundinclude those compounds composed of the above-mentioned known electrontransporting compounds such as quinolinol derivative metal complex suchas Alq₃ (trisquinolinol aluminum), oxadiazole derivatives, and triazolederivatives to which at least one polymerizable functional group, suchas a (meth)acrylic group, a vinyl group, a styryl group, an isocyanategroup, or a thiocyanate group, is bonded. Specific examples thereofinclude bisquinolinol methacryloyloxy quinolinol aluminum, quinolinolbismethacryloyloxy quinolinol aluminum, methacryloyloxy oxadiazole,styryl oxadiazole, bisstyryl oxadiazole and the like. In the case of thepolymerizable electron transporting compound, crosslinking polymerizableelectron transporting compounds such as quinolinol bismethacryloyloxyquinolinol aluminum and bisstyryl oxadiazole are preferred.

[0494] The composition containing a polymerizable light emittingcompound for use in the polymer light emitting material of the presentinvention may contain other polymerizable compounds. The existence ofother polymerizable compounds in the composition is preferable sincesuch increases the freedom in selecting the composition.

[0495] Other polymerizable compounds are not particularly limited as faras they do not inhibit light emission of the polymer light emittingmaterial of the present invention. Examples thereof include methylmethacrylate, ethyl acrylate, ethylene glycol dimethacrylate, propyleneglycol diacrylate, trimethylolpropane triacrylate, styrene, stilbene andthe like. In the case of other polymerizable compounds, crosslinkingcompounds such as ethylene glycol dimethacrylate, propylene glycoldiacrylate, trimethylolpropane triacrylate and stilbene are preferred.

[0496] The polymerizable composition for use in the polymer lightemitting material of the present invention may contain a polymerizationinitiator. Any polymerization initiator may be used without particularlimitations as far as it can initiate the polymerization of theabove-mentioned polymerizable functional groups. Depending on themechanism of polymerization of the polymerizable functional group, aradical polymerization initiator, a cation polymerization initiator, ananion polymerization initiator and the like can be used. A radicalpolymerization initiator is preferred. Further, classifying thepolymerization initiators by the mechanism of their activation, athermal polymerization initiator and an optical polymerization initiatorcan be used. The optical polymerization initiator as used herein refersto those that initiate polymerization by actinic rays such as visiblelight, ultraviolet ray, electron beam, and gamma ray.

[0497] Examples of the thermal radical polymerization initiator includeazo compounds such as 2,2′-azobisisobutyronitrile (AIBN) and2,2′-azobisisovaleronitrile, ketone peroxides such as methyl ethylketone peroxide, methyl isobutyl ketone peroxide, and cyclohexanoneperoxide, diacyl peroxides such as benzoyl peroxide, decanoyl peroxide,and lauroyl peroxide, dialkyl peroxides such as dicumyl peroxide,t-butyl cumyl peroxide, and di-t-butyl peroxide, peroxy ketals such as1,1-bis(t-hexyl-peroxy)-3,3,5-trimethylcyclohexane,1,1-di-t-butylperoxy-cyclohexane, and 2,2-(di-t-butylperoxy)butane,alkyl peroxy esters such as t-butyl peroxypivalate, t-butylperoxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, di-t-butyl peroxyazelate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butyl peroxyacetate, t-butylperoxybenzoate, di-t-butyl peroxytrimethyladipate, t-butylperoxy-2-ethylhexanoate, t-hexyl peroxy-2-ethyl-hexanoate, percarbonatessuch as diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate,and t-butyl peroxyisopropyl-carbonate, and the like.

[0498] Examples of the optical radical polymerization initiator includeacetophenone, acetophenone derivatives such as2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone,1-hydroxycyclohexylphenylketone,2-methyl-1-[4-(methylthio)-phenyl]-2-morpholino-1-propanone,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, and2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, benzophenonederivatives such as 4,4′-bis(dimethylamino)benzophenone, and4-trimethylsilylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide,benzoin, benzoin derivatives such as benzoin ethyl ether, benzoin propylether, benzoin isobutyl ether, and benzoin isopropyl ether, methylphenyl glyoxylate, benzoin dimethyl ketal,2,4,6-trimethylbenzoyldiphenylphosphine oxide, and so forth.

[0499] The use amount of the polymerization initiators is in a range offrom 0.001 to 5 mass % and preferably from 0.01 to 1 mass %, based onthe weight of the polymerizable composition of the present invention.

[0500] The polymerizable composition containing at least one lightemitting compound of the present invention can be formed in a form of afilm on a layer that serves as a base by a coating method. The layerthat serves as a base may vary depending on the construction of theorganic light emitting device. In the case of the device shown in FIG.1, the hole transporting layer 3 serves as a base layer, and in Examples19 to 22, an ITO anode serves as a base layer. Upon coating thepolymerizable composition containing at least one light emittingcompound of the present invention on a base layer, the composition mayalso be coated after diluting it with a solvent. The dilution with asolvent can decrease the viscosity of the composition so that the filmthickness can be reduced. The solvent used can be removed by a treatmentsuch as heating or reduction in pressure before, during or after thepolymerization.

[0501] Although it is not generally limited, the thickness of the lightemitting layer composed of the polymer light emitting material of thepresent invention is preferably from 1 nm to 10 μm and more preferablyfrom 5 nm to 1 μm.

[0502] A layer containing a light emitting material for organic lightemitting device of the present invention can be prepared by forming (forexample, by coating) a composition containing a polymer light emittingmaterial into a form of a film on a layer that serves as a base for anorganic EL device, or by forming a polymerizable composition containingat least one light emitting compound into a form of a film on a layerthat serves as a base for an organic EL device and then polymerizing itto form a polymer.

[0503] The layer containing a light emitting material for organic lightemitting device as used herein means (1) a layer containing only a lightemitting material, (2) a layer containing a hole transporting material,a light emitting material and an electron transporting material, (3) alayer containing a hole transporting material and a light emittingmaterial, or (4) a layer containing a light emitting material and anelectron transporting material.

[0504] When a polymer light emitting material has a crosslinkedstructure, it is difficult that the polymer obtained by polymerizing isformed into a film under normal conditions. In the case where thecrosslinkable compound having two or more polymerizable functionalgroups is homopolymerized by a solution polymerization method, thecrosslinked polymer precipitates in the solvent as insoluble matter.Therefore, the crosslinked polymer in film form can be produced bydissolving a polymerizable light emitting compound into a solvent orother liquid monomers, forming it into a film by printing methods suchas a spin coating method, dip coating and ink jet printing method,screen printing method and micro gravure method, and then polymerizingit.

[0505] In the case of copolymerizing of the crosslinkable compound witha large amount of monofunctional monomers, copolymer having a solubilityto the solvent can be obtained and be coated on a substrate of anorganic light emitting device in liquid state. In this case, themonofunctional monomer must be used in large excess to an amount of thecrosslinkable compound.

[0506] In the organic light emitting device of the present invention,formation of a hole transport layer and an electron transport layer onthe both sides or one side of the light emitting layer can furtherimprove the light emission efficiency and/or durability of the device.

[0507] As the hole transport material for forming a hole transportlayer, known hole transport materials such as triphenylaminederivatives, e.g., TPD(N,N′-diphenyl-N,N′-(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine), α-NPD(4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl), and m-MTDATA(4,4′,4″-tris(3-methylphenylphenylamino)triphenylamine), andpolyvinyl-carbazole may be used. These hole transporting materials maybe used singly or in admixture with or laminated on other holetransporting materials. The thickness of the hole transport layer alsodepends on the electroconductivity of the hole transport layer so thatit cannot be generally limited. However, it is preferably from 10 nm to10 μm and more preferably from 10 nm to 1 μm.

[0508] As the electron transporting material for forming an electrontransport layer, known electron transporting material, such asquinolinol derivatives metal complexes, e.g., Alq₃ (trisquinolinolaluminum), oxadiazole derivatives, and triazole derivatives may be used.However, the present invention is by no means limited thereto. Theelectron transporting materials may be used singly or in admixture withor laminated on other electron transporting materials. The thickness ofthe electron transport layer also depends on the electroconductivity ofthe electron transport layer so that it cannot be generally limited.However, it is preferably from 10 nm to 10 μm and more preferably from10 nm to 1 μm.

[0509] The light emitting material, hole transport material and electrontransport material used in the above-mentioned light emitting layer canbe used singly for forming each layer. In addition, the polymer materialmay be used as a binder for forming each layer. Examples of the polymermaterial used for this purpose include polymethyl methacrylate,polycarbonate, polyester, polysulfone, polyphenylene oxide and the like.However, the present invention is by no means limited thereto.

[0510] The light emitting material, hole transporting material andelectron transporting material used in the above-mentioned lightemitting layer can be formed into a film by using various methods suchas a resistance heating vapor deposition method, an electron beam vapordeposition method, a sputtering method, a coating method, a solutioncoating method, and a printing method and the present invention is notparticularly limited thereto. In the case of low molecular weightcompounds, mainly resistance heating vapor deposition and electron beamvapor deposition are frequently used. In the case of polymer materials,mainly a casting method and a solution casting method are frequentlyused.

[0511] As the anode material of the organic light emitting device of thepresent invention, known transparent electroconductive materials such asITO (indium tin oxide), tin oxide, zinc oxide, electroconductivepolymers, e.g., polythiophene, polypyrrole and polyaniline can be used.However, the present invention is not particularly limited thereto. Thesurface resistance of the electrode made of such a transparentelectroconductive material is preferably 1 to 50 Ω/□ (ohm/square). Suchan anode material can be formed into a film by various methods such asan electron bean vapor deposition method, a sputtering method, achemical reaction method, and a coating method. However, the presentinvention is not particularly limited thereto. The thickness of theanode is preferably from 50 to 300 nm.

[0512] For the purpose of relaxation of the injection barrier wall, abuffer layer may be inserted between the anode and a hole transportlayer or between the anode and an organic layer laminated adjacent tothe anode. For the buffer layer, known materials such as copperphthalocyanine and polyethylene dioxythiophene may be used. However, thepresent invention is not particularly limited thereto.

[0513] As the cathode material of the organic light emitting device ofthe present invention, known cathode materials, for example, Al, Mg—Agalloys, alkaline earth metals such as Ca, alloys of Al and an alkalinemetal, such as Al—Ca, and the like maybe used. However, the presentinvention is not particularly limited thereto. As the method of forminga film of these cathode materials, a resistance heating vapor depositionmethod, an electron beam vapor deposition method, a sputtering method,an ion plating method and the like can be used. However, the presentinvention is not particularly limited thereto. The thickness of thecathode is preferably from 10 nm to 1 μm and more preferably from 50 to500 nm.

[0514] For the purpose of improving the efficiency of electroninjection, an insulating layer having a thickness of 0.1 to 10 nm may beinserted between the cathode and an electron transport layer or betweenthe cathode and an organic layer laminated adjacent to the cathode. Forthe insulating layer, known cathode materials such as lithium fluoride,magnesium fluoride, magnesium oxide, and alumina may be used. However,the present invention is not particularly limited thereto.

[0515] Furthermore, in order to prevent holes to pass through the lightemitting layer and allow holes to efficiently recombine with electronswithin the light emitting layer, a hole blocking layer maybe providedadjacent to the cathode side of the light emitting layer. For formingsuch a hole blocking layer, known materials such as triazole derivativesand oxadiazole derivatives may be used. However, the present inventionis not particularly limited thereto.

[0516] As the substrate of the organic light emitting device of thepresent invention, an insulating substrate transparent to the emissionwavelength of the light emitting material may be used. As such, knownmaterials such as transparent plastics including PET (polyethyleneterephthalate) and polycarbonate as well as glass may be used. However,the present invention is not particularly limited thereto.

[0517] The organic light emitting device of the present invention canconstitute a matrix-type or segment-type pixels by a known method. Also,it can be used as a backlight without forming pixels.

[0518] However, the present invention is not particularly limitedthereto.

BEST MODE FOR CARRYING OUT THE INVENTION

[0519] Hereinafter, the present invention will be described in moredetail by referring to typical examples. However, the examples aremerely exemplary for the purpose of explanation and the presentinvention should by no means be limited thereto.

[0520] <Measurement Apparatus, etc.>

[0521] 1) ¹H-NMR

[0522] JNM EX270 manufactured by JEOL, Ltd.

[0523] 270 MHz

[0524] Solvent: chloroform-d₁ or dimethyl sulfoxide-d₆

[0525] 2) GPC Measurement (Measurement of Molecular Weight)

[0526] Column: Shodex KF-G+KF804L+KF802+KF801

[0527] Eluent: Tetrahydrofuran (THF)

[0528] Temperature: 40° C.

[0529] Detector: RI (Shodex RI-71)

[0530] 3) Elementary Analysis Equipment

[0531] Model CHNS-932, manufactured by LECO

[0532] 4) ICP Elementary Analysis

[0533] ICPS 8000, manufactured by Shimadzu Corporation

[0534] <Reagents>

[0535] Unless otherwise indicated specifically, commercially availablepreparation (reagent grade) was used without purification.

EXAMPLE 1 Synthesis of Polymerizable compound Ir(3-MA-PPy).(3-PrCO-PPy)₂

[0536] (1) 2-(3-Methoxyphenyl)pyridine (3-MeO-PPy) was synthesized by aconventional method.

[0537] That is, as shown in the reaction scheme below,(3-methoxyphenyl)magnesium bromide was synthesized from 22.4 g (120mmol) of 3-bromoanisole with 3.4 g of magnesium in dry tetrahydrofuran(THF) in an argon stream by a conventional manner. This was slowly addedto a dry THF solution of 15.8 g (100 mmol) of 2-bromopyridine and 1.8 gof (1,2-bis(diphenylphosphino)-ethane)dichloronickel (II) (Ni(dppe)Cl₂)and the mixture was stirred at 50° C. for 1 hour. After adding 250 ml of5% hydrochloric acid aqueous solution to the reaction mixture, thereaction mixture was extracted with chloroform to obtain a targetsubstance and the organic layer was distilled under reduced pressure.17.4 g (93.9 mmol) of 2-(3-methoxyphenyl)pyridine (3-MeO-PPy) wasobtained as a colorless transparent liquid. Identification was performedby CHN elementary analysis and ¹H-NMR.

[0538]¹H-NMR (CDCl₃, ppm): δ 8.68 (d, 1H), 7.72 (m, 2H), 7.59 (s, 1H),7.54 (d, 1H), 7.37 (t, 1H), 7.22 (d,1H), 6.97 (d, 1H), 3.89 (s, 3H).Elementary analysis Calcd: C 77.81, H 5.99, N 7.56. Found: C 77.44, H6.01, N 7.53.

[0539]

[0540] (2) Then, 3-MeO-PPy thus obtained andtris(acetyl-acetonato)iridium (III) (Ir(acac)₃) were allowed to react ata high temperature as shown in the reaction scheme below to synthesizetris[2-(3-methoxyphenyl)pyridine]iridium (III) (Ir(3-MeO-PPy)₃).

[0541] That is, 5.00 g (27.0 mol) of3-MeO-PPy and 2.0 g (4.1 mmol) ofIr(acac)₃ were allowed to react in 200 ml of glycerol at 250° C. for 9hours and purified using column chromatography to obtain 0.400 g (0.54mmol) of Ir(3-MeO-PPy)₃ as yellow powder.

[0542] Repeating the above-mentioned operation 8 times afforded 3.20 g(4.32 mmol) in total of Ir(3-Meo-PPy)₃.

[0543] Identification of the product was performed by ¹H-NMR and CHNelementary analysis.

[0544]¹H-NMR (CDCl₃, ppm): δ 7.82(d, 3H), 7.56(t, 3H), 7.53(s, 3H),7.25(d, 3H), 6.84(t, 3H), 6.67(d,3H), 6.60(d, 3H), 3.80(s, 9H).Elementary analysis Calcd: C 58.05, H 4.06, N 5.64. Found: C 57.60, H4.17, N 5.57.

[0545]

[0546] (3) The Ir(3-MeO-PPy)₃ thus obtained was subjected to hydrolysisin an aqueous solution of hydrochloric acid by a conventional method toconvert the methoxy groups to hydroxyl groups to obtain[2-(3-hydroxyphenyl)pyridine]iridium (III) (Ir(3-HO-PPy)₃) as powder asshown in the reaction scheme below.

[0547] (4) Ir(3-HO-PPy)₃ was allowed to react with methacryloyl chloridein a molar ratio of 1:1 by the reaction scheme below to esterify a partof the hydroxyl groups thereof, thereby synthesizing a complex composedmainly of Ir(3-MA-PPy)(3-Ho-PPy)₂. Then, the remaining hydroxyl groupswere allowed to react with propionyl chloride (PrCOCl) to obtain acomplex composed mainly of Ir(3-MA-PPy)(3-PrCO-PPy)₂.

[0548] That is, after charging 32 ml of dry THF, 2.81 g (4 mmol) ofIr(3-HO-PPy)₃ and 2.40 g (23.6 mmol) of triethylamine as a base in areactor, a solution of 0.424 g (4 mmol) of methacryloyl chloride in 16ml of dry THF was dripped over 30 minutes and the mixture was stirred at20° C. for 5 hours. To this reaction mixture, a solution of 1.48 g (16mmol) of propionyl chloride in 16 ml of dry THF was dripped over 30minutes, followed by reaction of the resulting mixture at 20° C. for 5hours to esterify the remaining hydroxyl groups to react. Thentriethylamine hydrochloride was filtered off. The solvent in thefiltrate was evaporated to dryness and the solid component was purifiedby recrystallization from chloroform/methanol mixed solvent 2 times toafford 2.305 g (2.60 mmol) of the objective compoundIr(3-MA-PPy)(3-PrCO-PPy)₂ as powder. Identification of the product wasperformed by ¹H-NMR and CHN elementary analysis.

[0549]¹H-NMR (CDCl₃, ppm): δ 7.82(m, 3H), 7.56(m, 6H), 7.26(m, 3H),6.84(m, 3H), 6.67(m,3H), 6.61(m, 3H), 6.35(s, 1H), 5.74(s, 1H), 2.67(q,4H), 2.08(s, 3H), 1.42(t, 6H). Elementary analysis Calcd: C 58.49, H4.11, N 4.76. Found: C 58.13, H 4.10, N 4.72.

[0550]

EXAMPLE 2 Synthesis of Ir(3-MA-PPy)(3-PrCO-PPy)₂ Polymer

[0551] In a reactor were charged 2.22 g (2.5 mmol) ofIr(3-MA-PPy)(3-PrCO-PPy)₂ complex synthesized in Example 1, 0.010 g(0.061 mmol) of 2,2′-azobis (isobutyronitrile) (AIBN), and 30 ml ofbutyl acetate and the atmosphere was exchanged with nitrogen.Thereafter, the mixture was allowed to react at 80° C. for 10 hours (cf.Reaction Scheme below). After completion of the reaction, the reactionmixture was dripped into acetone to perform reprecipitation and theresultant polymer was recovered by filtration. A procedure ofreprecipitation by dripping a chloroform solution of the recoveredpolymer into methanol was further repeated 2 times to purify thepolymer, which was then recovered and dried in vacuum to afford 1.85 gof the objective Ir(3-MA-PPy)(3-PrCO-PPy)₂ polymer as powder. Theelementary analysis of C, H, N and Ir of the obtained polymer indicatedthat the polymer had the same composition as Ir(3-MA-PPy)(3-PrCO-PPy)₂.The weight average molecular weight of the polymer was 8,000 in terms ofpolystyrene (by GPC measurement using HFIP (hexafluoroisopropanol) as aneluent).

EXAMPLE 3 Synthesis of Polymerizable compound Ir(3-MOI-PPy)(3-PrCO-PPy)₂

[0552] A monomer intermediate Ir(3-HO-PPy)₃ synthesized in the samemanner as in Example 1 was allowed to react with 2-methacryloyloxyethylisocyanate (Trade name “Karenz MOI”, manufactured by Showa Denko K. K.,hereinafter sometimes referred to as “MOI”) in a ratio of 1:1 (molarratio) and then the remaining hydroxyl groups were allowed to react withPrCOCl to obtain a complex composed mainly ofIr(3-MOI-PPy)(3-PrCO-PPy)₂.

[0553] That is, in a reactor were charged 32 ml of dry THF, 2.81 g (4mmol) of Ir(3-HO-PPy)₃, and 0.636 g (4 mmol) of MOI, and after additionof a catalyst amount of dibutyltin (IV) dilaurate, the mixture wasallowed to react at 20° C. for 5 hours. To this reaction mixture wasadded 2.400 g (24.5 mmol) of triethylamine as a base. Thereafter, asolution of 1.48 g (16 mmol) of propionyl chloride in 16 ml of dry THFwas dripped over 30 minutes, followed by reaction at 20° C. for 5 hoursto react the remaining hydroxyl groups. Then triethylamine hydrochloridewas filtered off. The solvent in the filtrate was evaporated to drynessand the solid component was purified by performing recrystallizationfrom chloroform/methanol mixed solvent 2 times to afford 2.62 g (2.70mmol) of the objective compound Ir(3-MOI-PPy)(3-PrCO-PPy)₂ as powder.Identification of the product was performed by ¹H-NMR and CHN elementaryanalysis.

[0554]¹H-NMR (CDCl₃, ppm): δ 7.82(m, 3H), 7.56(m, 6H), 7.26(m, 3H),6.84(m, 3H), 6.67(m,3H), 6.61(m, 3H), 6.14(s, 1H), 5.61(s, 1H), 5.23(br,1H), 4.29(t, 2H), 3.58(m, 2H), 2.66(q, 4H), 1.95(s, 3H), 1.41(t, 6H).Elementary analysis Calcd: C 56.95, H 4.26, N 5.78. Found: C 56.58, H4.25, N 5.72.

[0555]

EXAMPLE 4 Synthesis of Ir(3-MOI-PPy)(3-PrCO-PPy)₂ polymer

[0556] In a reactor were charged 2.43 g (2.5 mmol) ofIr(3-MOI-PPy)(3-PrCO-PPy)₂ complex synthesized in Example 1, 0.010 g(0.061 mmol) of 2,2′-azobis(isobutyronitrile) (AIBN), and 30 ml of butylacetate and the atmosphere was exchanged with nitrogen. Thereafter, themixture was allowed to react at 80° C. for 10 hours (cf. Reaction Schemebelow).

[0557] After completion of the reaction, the reaction mixture wasdripped into acetone to perform reprecipitation and the resultantpolymer was recovered by filtration. A procedure of reprecipitation bydripping a chloroform solution of the recovered polymer into methanolwas further repeated 2 times to purify the polymer, which was thenrecovered and dried in vacuum to afford 2.05 g of the objectiveIr(3-MOI-PPy)(3-PrCO-PPy)₂ polymer as powder. The elementary analysis ofC, H, N and Ir of the obtained polymer indicated that the polymer hadsubstantially the same composition as Ir(3-MOI-PPy)(3-PrCO-PPy)₂. Theweight average molecular weight of the polymer was 18,000 in terms ofpolystyrene (by GPC measurement using HFIP (hexafluoroisopropanol) as aneluent).

EXAMPLE 5 Synthesis of (HPPy) Polymer Ir/PPy Complex

[0558] As shown in Reaction Scheme below, 1.98 g (5.00 mmol) of5-bromo-2-(4-bromo-3-hexylphenyl)pyridine (HPPyBr₂) was polymerized in10 ml of N,N-dimethylformamide (DMF) with bis(cyclooctadine)nickel(0)(Ni(COD)₂), cyclooctadiene (COD) and 2,2′-bipyridine as catalysts by aconventional method to synthesize hexylphenylpyridine polymer (HPPypolymer).

[0559] Then, 0.625 g (4 mmol) of the HPPy polymer and 0.099 g (0.2 mmol)of Ir(acac)₃ were dissolved in m-cresol and allowed to react at 250° C.for 10 hours. Further, to this solution was added 0.062 g (0.4 mmol) of2-phenylpyridine (PPy) and the mixture was allowed to react at 250° C.for 10 hours. After completion of the reaction, the reaction mixture wasdripped into acetone to perform reprecipitation and the obtained polymerwas recovered by filtration. A procedure of reprecipitation by drippinga DMF solution of the recovered polymer into acetone was furtherrepeated 2 times to purify the polymer, which was then recovered anddried in vacuum to afford 0.564 g of the objective (HPPy) Polymer Ir/PPycomplex as powder. The elementary analysis of C, H, N and Ir of theobtained polymer supported the presumed structure of the polymer. Theweight average molecular weight of the polymer was 23,000 in terms ofpolystyrene (by GPC measurement using HFIP (hexafluoroisopropanol) as aneluent).

EXAMPLE 6 TO 8 Fabrication and Evaluation of Organic Light EmittingDevices

[0560] Mass % hexafluoroisopropanol (HFIP) solutions of threephosphorescent polymers synthesized in Examples 2, 4 and 5, i.e.,Ir(3-MA-PPy)(3-PrCO-PPy)₂ polymer, Ir(3-MOI-PPy)(3-PrCO-PPy)₂ polymer,and (HPPy) polymer Ir/PPy complex, respectively, were each coated in asize of 5 mm×5 mm by a spin coating method on an ITO anode (ITO-coatedglass substrate) on which polyethylenedioxythiophene (PEDOT,manufactured by Bayer AG) had been preliminarily coated to a thicknessof 500 Angstroms and dried by heating at 80° C. in vacuum for 10 hoursto form phosphorescent polymer layer having a thickness of about 1,000Angstroms on the PEDOT/ITO anode for each polymer.

[0561] On the three types of (two for each) phosphorescentpolymer/PEDOT/ITO electrodes, a layer of PBD(2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole) was formed asan electron transport layer to a thickness of about 500 Angstroms byvacuum deposition. Subsequently, on the electron transport layer wasformed a layer of Ag/Mg in atomic ratio of 1/10 to a thickness of about1,000 Angstroms to fabricate 6 (two for each polymer) organic lightemitting devices. To these devices attached lead wires under argonatmosphere in a glove box and the devices were sealed in a glass tubeunder argon atmosphere and used for evaluation of luminescence.

[0562] The luminance of the devices was measured by using a luminancemeter BM-8, manufactured by Topcon Corporation while applying a voltageto the organic light emitting device using a programmable directvoltage/current source TR6143, manufactured by Advantest Corporation.

[0563] When the DC voltage was applied, luminescence starting voltage,initial luminance at a voltage of 10 V and luminance after 240 hours'consecutive luminescence with a fixed voltage of 10 V were obtained asshown in Table 1 (as an average of the two devices for each polymer).

COMPARATIVE EXAMPLES 1 AND 2 Fabrication and evaluation of organic lightemitting devices

[0564] Four (two for each polymer) of organic light emitting deviceswere fabricated in the same manner as in Example 6, 7 and 8 except that5 mass % chloroform solutions of intermediate complex Ir(3-MeO-PPy)₃synthesized in Example 1 and PMMA (poly(methyl methacrylate)) in placeof the 5 mass % HFIP solutions of the three phosphorescent polymers usedin Examples 6, 7 and 8 in proportions shown in Table 2. When a DCvoltage was applied to the fabricated devices in the same manner as inExamples 6, 7 and 8, luminescence starting voltage was 10 V and 11 V,respectively. Initial luminance at a voltage of 12 V, and luminanceafter 240 hours' consecutive luminescence with a fixed voltage of 12 Vwere as shown in Table 2 (as an average of the two devices for eachpolymer). TABLE 1 10 V Luminance (Cd/m²) Luminescence After Exam-Phosphorescent Starting 240 ple Polymer Voltage (V) Initial Hours 6Ir(3-MA-PPy) 5 1280 1180 (3-PrCO—PPy)₂ Polymer 7 Ir(3-MOI—PPy) 6 14501250 (3-PrCO—PPy)₂ Polymer 8 (HPPy) Polymer 3 730 680 Ir/PPy Complex

[0565] TABLE 2 Luminescence 12 V Luminance (Cd/m²) Comparative Complex(Ir(3-MeO—PPy)₃)/PMMA Starting After 240 Example (Mass Ratio) Voltage(V) Initial Hours 1 1/5 10 150 70 2 1/2 11 120 50

EXAMPLE 9 Fabrication and Evaluation of an Organic Light Emitting Deviceusing a Light Emitting Composition Composed of a Phosphorescent PolymerCompound and a Hole Transporting Polymer Compound

[0566] 3 mass % chloroform solution of the phosphorescent polymersynthesized in Example 4, i.e., Ir(3-MOI-PPy)(3-PrCO-PPy)₂ polymer andpoly(N-vinylcarbazole) was prepared. The solution contained the polymersin a ratio of 70 mass % of the Ir(3-MOI-PPy)(3-PrCO-PPy)₂ polymer to 30mass % of the poly(N-vinylcarbazole). Two organic light emitting deviceswere fabricated in the same manner as in Examples 6, 7 and 8 except thatthis solution was used in place of the 5 mass % HFIP solutions of thethree phosphorescent polymer used in Examples 6, 7 and 8. When a DCvoltage was applied to the fabricated devices in the same manner as inExamples 6, 7 and 8, the luminescence starting voltage was 5 V and theluminance at 12 V was 1,860 cd/m², and the luminance after 240 hours'consecutive luminescence at a fixed voltage of 12 V was 1, 690 cd/m² (asan average of the two devices for each polymer).

EXAMPLE 10 Fabrication and Evaluation of an Organic Light EmittingDevice using a Light Emitting Composition Composed of a PhosphorescentPolymer Compound and an Electron Transporting Low Molecular WeightCompound

[0567] 4 mass % chloroform solution of the phosphorescent polymersynthesized in Example 4, i.e., Ir(3-MOI-PPy)(3-PrCO-PPy)₂ polymer andPBD was prepared. The solution contained the polymers in a ratio of 70mass % of the Ir(3-MOI-PPy)(3-PrCO-PPy)₂ polymer to 30 mass % of thePBD. This solution was coated in a size of 5 mm×5 mm by a spin coatingmethod on an ITO anode (ITO-coated glass substrate) on whichpolyethylenedioxythiophene (PEDOT, manufactured by Bayer AG) had beenpreliminarily coated to a thickness of 500 Angstroms and dried byheating at 80° C. in vacuum for 10 hours to form phosphorescent polymercomposition layer having a thickness of about 1,000 Angstroms on thePEDOT/ITO anode. Subsequently, on each the phosphorescent polymercomposition layer was formed a film of Ag/Mg (weight ratio: 9/1) as acathode to a thickness of about 1,000 Angstroms to fabricate two organiclight emitting devices. To these devices were attached lead wires in anargon atmosphere in a glove box and the devices were sealed in a glasstube in an argon atmosphere and used for evaluation of luminescence.When a DC voltage was applied to the fabricated devices in the samemanner as in Examples 6, 7 and 8, the luminescence starting voltage was6 V and the luminance at 12 V was 1,580 cd/m², and the luminance after240 hours' consecutive luminescence at a fixed voltage of 12 V was 1,340cd/m² (as an average of the two devices for each polymer).

EXAMPLE 11 Fabrication and Evaluation of an Organic Light EmittingDevice using a Light Emitting Composition Composed of a PhosphorescentPolymer Compound and an Electron Transporting Polymer Compound

[0568] 3 mass % chloroform solution of the phosphorescent polymersynthesized in Example 4, i.e., Ir(3-MOI-PPy)(3-PrCO-PPy)₂ polymer andthe poly PBD synthesized by the method disclosed in Japanese PatentApplication Laid-open No. 10-1665 was prepared. The solution containedthe polymers in a ratio of 70 mass % of the Ir(3-MOI-PPy)(3-PrCO-PPy)₂polymer to 30 mass % of the poly PBD. Two organic light emitting deviceswere fabricated in the same manner as in Example 10 except that thissolution was used in place of the 5 mass % chloroform solution of thephosphorescent polymer and PBD used in Example 10. When a DC voltage wasapplied to the fabricated devices in the same manner as in Examples 6, 7and 8, the luminescence starting voltage was 5 V and the luminance at 12V was 1,710 cd/m², and the luminance after 240 hours' consecutiveluminescence at a fixed voltage of 12 V was 1, 580 cd/m² (as an averageof the two devices for each polymer).

EXAMPLE 12 Synthesis of Polymerizable Light Emitting CompoundIr(3-MA-PPy)₃

[0569] In the same manner as in the synthesis described in Example 1,Ir(3-MeO-PPy)₃ was subjected to hydrolysis of methoxy groups in anaqueous solution of hydrochloric acid to convert them into hydroxylgroups to obtain tris (3-hydroxyphenylpyridine) iridium (III)(Ir(3-HO-PPy)₃) as powder (cf. Reaction Scheme below) Then,Ir(3-HO-PPy)₃ was allowed to react with methacryloyl chloride in a molarratio of 1:3 to esterify all the hydroxyl groups thereof to synthesizean Ir(3-MA-PPy)₃ complex.

[0570] That is, in a reactor were charged 32 ml of dry THF, 2.81 g (4mmol) of Ir(3-HO-PPy)₃ and 2.40 g (23.6 mmol) of triethylamine as a baseand a solution of 1.293 g (12.2 mmol) of methacryloyl chloride in 32 mlof dry THF was dripped over 90 minutes to perform reaction at 20° C. for5 hours. The precipitated triethylamine hydrochloride was filtered offand the solvent in the filtrate was evaporated to dryness. The obtainedsolid component was purified by performing recrystallization from amixed solvent of hexafluoroisopropanol/methanol two times to obtain2.805 g (3.08 mmol) of the objective trifunctional Ir(3-MA-PPy)₃ aspowder. Identification of the product was performed by ¹H-NMR and CHNelementary analysis.

[0571]¹H-NMR (CDCl₃, ppm): δ 7.82(d, 3H), 7.58(t, 3H), 7.55(s, 3H),7.26(d, 3H), 6.86(t, 3H), 6.67(d,3H), 6.63(d, 3H), 6.36(s, 3H), 5.74(s,3H), 2.09(s, 9H). Elementary analysis Calcd: C 59.59, H 4.00, N 4.63.Found: C 59.21, H 3.98, N 4.58.

[0572]

EXAMPLE 13 Synthesis of Polymerizable Light Emitting CompoundIr(3-MOI-PPy)₂(3-PrCO-PPy)

[0573] The monomer intermediate Ir(3-HO-PPy)₃ synthesized in the samemanner as in Example 1 was allowed to react with 2-methacryloyloxyethylisocyanate (Trade name “Karenz MOI”, manufactured by Showa Denko K. K.,hereinafter sometimes referred to as “MOI”) in a ratio of 1:3 (by mole)and the remaining OH group was allowed to react with propionyl chloride(PrCOCl) to obtain an Ir(3-MOI-PPy)₂(3-PrCO-PPy) complex.

[0574] That is, in a reactor were charged 48 ml of dry THF and 2.81 g (4mmol) of Ir(3-HO-PPy)₃ and 1.272 g (8 mmol) of MOI and a catalyst amountof dibutyltin (IV) dilaurate was added thereto, and the mixture wasallowed to react at 20° C. for 5 hours. After adding 2.400 g (24.5 mmol)of triethylamine as a base to the reaction mixture, a solution of 0.74 g(8.0 mmol) of PrCOCl in 8 ml of dry THF was dripped over 30 minutes andthe mixture was allowed to react at 20° C. for additional 5 hours toesterify the remaining hydroxyl groups. The precipitated triethylaminehydrochloride was filtered off and the solvent in the filtrate wasevaporated to dryness. The obtained solid component was purified byperforming recrystallization from a mixed solvent of chloroform/methanoltwo times to obtain 2.75 g (2.57 mmol) of the objectiveIr(3-MOI-PPy)₂(3-PrCO-PPy) as powder. Identification of the product wasperformed by ¹H-NMR and CHN elementary analysis.

[0575]¹H-NMR (CDCl₃, ppm): δ 7.81(m, 3H), 7.54(m, 6H), 7.26(m, 3H),6.86(m, 3H), 6.68(m,3H), 6.59(m, 3H), 6.13(s, 2H), 5.60(s, 2H), 5.22(br,2H), 4.27(t, 4H), 3.57(m, 4H), 2.67(q, 2H), 1.95(s, 6H), 1.41(t, 3H).Elementary analysis Calcd: C 56.17, H 4.34, N 6.55. Found: C 55.86, H4.37, N 6.51.

[0576]

EXAMPLES 14 TO 19 Fabrication and Evaluation of Organic Light EmittingDevices using Polymerizable Compositions

[0577] 10 Mass % chloroform solutions of combinations of the fourphosphorescent polymerizable compounds synthesized in Examples 1, 3, 12and 13, i.e., monofunctional Ir(3-MA-PPy)(3-PrCO-PPy)₂, monofunctionalIr(3-MOI-PPy)(3-PrCO-PPy)₂, trifunctional (3-MOI-PPy)₃, and bifunctional(3-MOI-PPy)₂(3-PrCO-PPy), respectively as shown in Table 3 wereprepared. After addition of AIBN (azobisbutyronitrile) as apolymerization initiator in an amount of 2 mass parts per 100 mass partsof the total amount of the monomers, each of the solutions was coated inan area of a size of 5 mm×5 mm by a spin coating method on an ITO anode(ITO-coated glass substrate) on which polyethylenedioxy-thiophene(PEDOT, manufactured by Bayer AG) had been preliminarily coated to athickness of 500 Angstroms. This was dried by heating at 60° C. for 2hours to polymerize and cure each monomer and further dried at 80° C.under reduced pressure for 8 hours to form phosphorescent polymer layerhaving a thickness of about 1,000 Angstroms on the PEDOT/ITO anode foreach combination.

[0578] On each of the six types of (total twelve) phosphorescentpolymer/PEDOT/ITO electrodes, a layer of TAZ(3-(4-biphenylyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole) wasformed as an electron transport layer to a thickness of about 500Angstroms by vacuum deposition. Subsequently, on the electron transportlayer was formed a layer of Ag/Mg (mass ratio: 9/1) as a cathode to athickness of about 1,000 Angstroms to fabricate 6 (two for each polymer)organic light emitting devices. To these devices were attached leadwires in an argon atmosphere in a glove box and the devices were sealedin a glass tube in an argon atmosphere and used for evaluation ofluminescence.

[0579] The luminance of the devices was measured by using a luminancemeter BM-8, manufactured by Topcon Corporation while applying a voltageto the organic light emitting device using a programmable directvoltage/current source TR6143, manufactured by Advantest Corporation.

[0580] When the DC voltage was applied, luminescence starting voltage,initial luminance at 10 V and luminance after 240 hours' consecutiveluminescence with a fixed voltage of 10 V were obtained as shown inTable 3 (as an average of the two devices for each polymer system).TABLE 3 10 V Luminance (Cd/m²) Luminescence After Monomers ofPhosphorescent Starting 240 Example Polymer (Molar Ratio) PolymerVoltage (V) Initial Hours Scheme 14 Ir(3-MA-PPy)/(3-PrCO—PPy)₂ Notcross- 5 1560 1150 (A) linked 15 Ir(3-MA-PPy)₃ Cross- 6 1430 1350 —linked 16 Ir(3-MA-PPy)(3- Cross- 5 1580 1420 (B)PrCO—PPy)₂/Ir(3-MA-PPy)₃(1/1) linked 17 Ir(3-MOI—PPy)(3-PrCO—PPy)₂ Notcross- 6 1600 1280 (C) linked 18 Ir(3-MOI—PPy)₂(3-PrCO—PPy) Cross- 61510 1380 — linked 19 Ir(3-MOI—PPy)(3-PrCO—PPy)₂/ Cross- 6 1600 1450 (D)Ir(3-MOI—PPy)₂(3-PrCO—PPy) linked (1/1)

[0581]

EXAMPLES 20 TO 23 AND COMPARATIVE EXAMPLE 3 Fabrication and Evaluationof Organic Light Emitting Devices using Polymerizable Compositions

[0582] Phenylpyridine (PPy) and tris (acetylacetonato) iridium (III)(Ir(acac)₃) were allowed to react at 300° C. by a conventional method tosynthesize a phosphorescent compound tris(phenylpyridine)iridium (III)(Ir(PPy)₃).

[0583] Electron transporting compound-added polymerizable luminescentcompound compositions as 10 mass % chloroform solutions were prepared bycombining the phosphorescent polymerizable compounds synthesized inExamples 1 and 12, i.e., monofunctional Ir(3-MA-PPy)(3-PrCO-PPy)₂ andtrifunctional (3-MOI-PPy)₃, respectively, and a bifunctional electrontransporting compound: bisstyryl oxadiazole (BSODA), and a comparativeelectron transporting compound: oxadiazole (ODA) as shown in Table 4were prepared. After addition of AIBN (azobisbutyronitrile) as apolymerization initiator in an amount of 2 mass parts per 100 mass partsof the total amount of the monomers, each of the solutions was coated inan area of a size of 5 mm×5 mm by a spin coating method on an ITO anode(ITO-coated glass substrate) on which polyethylenedioxythiophene (PEDOT,manufactured by Bayer AG) had been preliminarily coated to a thicknessof 500 Angstroms. This was dried by heating at 60° C. for 2 hours topolymerize and cure each monomer and further dried at 80° C. underreduced pressure for 8 hours to form phosphorescent polymer layer havinga thickness of about 1,000 Angstroms on the PEDOT/ITO anode for eachcombination.

[0584] On each of the five types of (total ten) phosphorescentpolymer/PEDOT/ITO electrodes, a layer of Ag/Mg (mass ratio: 9/1) as acathode was formed to a thickness of about 1,000 Angstroms to fabricatefive types of (two for each type) organic light emitting devices. Tothese devices were attached lead wires in an argon atmosphere in a glovebox and the devices were sealed in a glass tube in an argon atmosphereand evaluated for light emitting properties in the same manner as inExamples 14 to 19. TABLE 4 Phosphorescent Compound/Electron Luminescence10 V Luminance (Cd/m²) Transporting Compound Starting After (molarratio) Polymer Voltage (V) Initial 240 Hours Example 20 Ir(PPy)₃/BSODA(1/1) Crosslinked 6 1660 1120 Example 21 Ir(3-MA-PPy) Crosslinked 7 14801210 (3-PrCO—PPy)₂/BSODA(1/1) Example 22 Ir(3-MA-PPy)₃/ODA(1/1)Crosslinked 5 1380 1320 Example 23 Ir(3-MA-PPy) Not 5 1510 1080(3-PrCO—PPy)₂/ODA (1/1) crosslinked Comparative Ir(PPy)₃/ODA (1/1) Non-5 1680 880 Example 3 polymerized

EXAMPLE 25 Synthesis of a Polymerizable Compound Ir(MA-PPy)(PPy)₂

[0585] (1) The methoxy group of 3-MeO-PPy synthesized in the same manneras in Example 1 was hydrolyzed by a conventional method.

[0586] That is, as shown in Reaction Scheme below, 16.0 g (86.4 mmol) of3-MeO-PPy was dissolved in concentrated hydrochloric acid and stirred ina sealed vessel at 130° C. for 4 hours. After completion of thereaction, the reaction mixture was neutralized with an aqueous solutionof sodium hydrogen carbonate and the objective compound was extractedwith chloroform. Crystallization of the extract from a chloroform/hexanesolution afforded 10.4 g (60.7 mmol) of 2-(3-hydroxyphenyl)pyridine(3-HO-PPy) as colorless crystal. Identification was performed by ¹H-NMRand elementary analysis of C, H and N.

[0587]¹H-NMR (CDCl₃, ppm): δ 8.66(d, 1H), 7.76(t, 1H), 7.67(d, 1H),7.56(s, 1H), 7.40(d, 1H), 7.30(t, 1H), 7.26(t,1H), 6.88(d, 1H), 2.08(br,1H). Elementary analysis Calcd: C 77.17, H 5.30, N 8.18. Found: C 76.81,H 5.37, N 8.11.

[0588]

[0589] (2) The hydroxyl group of 3-HO-PPy was protected bytert-butyldimethylsilyl chloride (TBDMS-Cl) by a conventional method.

[0590] That is, as shown in the Reaction Scheme below, a solution of 8.6g (50.2 mmol) of 3-HO-PPy, 10.2 g of imidazole and 11.3 g (75.0 mmol) oftert-butyldimethylchlorosilane in 200 ml of N,N-dimethylformamide wasallowed to react at room temperature for 4 hours. Purification of thereaction mixture using a silica gel column afforded 13.0 g (45.5 mmol)of 2-(3-tert-butyldimethylsilyloxyphenyl)pyridine (³-SiO-PPy) as acolorless transparent liquid. Identification was performed by elementaryanalysis of C, H and N and ¹H-NMR.

[0591]¹H-NMR (CDCl₃, ppm): δ 8.68(d, 1H), 7.74(t, 1H), 7.68(d, 1H),7.58(d, 1H), 7.48(s, 1H), 7.32(t, 1H), 7.22(t, 1H), 6.89(d, 1H), 1.01(s,9H), 0.24(s, 6H). Elementary analysis Calcd: C 71.53, H 8.12, N 4.91.Found: C 71.08, H 8.14, N 4.88.

[0592]

[0593] (3) The 3-SiO-PPy was allowed to react withdi(μ-chloro)tetrakis(2-phenylpyridine)diiridium (III) ([Ir(PPy)₂Cl]₂)synthesized by a conventional method in the presence of silver (I)trifluoromethanesulfonate (AgCF₃SO₃).

[0594] That is, as shown in the Reaction Scheme below, 2.70 g ofAgCF₃SO₃ was added to a suspension of 5.71 g (20.0 mmol) of SiO-PPy and5.37 g (5.0 mmol) of [Ir(PPy)₂Cl]₂ in 5.37 g (5.0 mmol) of dry tolueneand refluxed for 6 hours. Purification of the reaction mixture using asilica gel column and then distilling off the solvent afforded 2.53 g(3.2 mmol) of (2-(3-tert-butyldimethylsilyloxyphenyl)pyridine)bis(2-phenylpyridine) iridium (III) (Ir(PPy)₂(3-SiO-PPy)) as yellowpowder. Identification was performed by elementary analysis of C, H andN and ¹H-NMR.

[0595]¹H-NMR (CDCl₃, ppm): δ 7.86(d, 2H), 7.78(d, 1H), 7.64(d, 2H),7.55(m, 6H), 7.16(s, 1H), 6.85(m,9H), 6.60(d, 1H), 6.45(d, 1H).Elementary analysis Calcd: C 59.67, H 4.88, N 5.35. Found: C 59.53, H4.89, N 5.34.

[0596]

[0597] (4) The silyl group of Ir(PPy)₂(3-SiO-PPy) was hydrolyzed by aconventional method.

[0598] That is, as shown in the Reaction Scheme below, 5.1 ml of a 1 MTHF solution of tetra-n-butylammonium fluoride (TBAF) was added to a THFsolution of 2.00 g (2.55 mmol) of Ir(PPy)₂(3-SiO-PPy) and the mixturewas allowed to react at room temperature for 30 minutes. Purification ofthe reaction mixture using a silica gel column and then distilling offthe solvent afforded 1.69 g (2.52 mmol) of (2-(3-hyroxyphenyl)pyridine)bis(2-phenylpyridine)iridium (III) (Ir(PPy)₂(3-HO-PPy)). Identificationwas performed by elementary analysis of C, H and N and ¹H-NMR.

[0599]¹H-NMR (CDCl₃, ppm): δ 7.87(d, 2H), 7.78(d, 1H), 7.6(m, 9H),6.85(m, 10H), 6.63(d, 1H), 4.23(s, 1H). Elementary analysis Calcd: C59.09, H 3.61, N 6.26. Found: C 58.64, H 3.74, N 6.17.

[0600]

[0601] (5) As shown in the Reaction Scheme below, 0.25 g (2.4 mmol) ofmethacryloyl chloride was added to a solution of 1.34 g (2.0 mmol) ofIr(PPy)₂(3-HO-PPy) and 0.81 g (8.0 mmol) of triethylamine as a base indry THF under argon stream and the mixture was allowed to react at 20°C. for 5 hours. Triethylamine hydrochloride was filtered from thereaction mixture and purification of the filtrate using a silica gelcolumn followed by distilling of the solvent afforded 1.28 g (1.73 mmol)of (2-(3-methacryloyloxyphenyl)pyridine) bis(2-phenylpyridine)iridium(III) (Ir(3-MA-PPy) (PPy)₂). Identification was performed by elementaryanalysis of C, H and N and ¹H-NMR.

[0602]¹H-NMR (CDCl₃, ppm): δ 7.87(d, 2H), 7.78(d, 1H), 7.6(m, 8H),7.40(s, 1H), 6.8(m, 10H), 6.59(d,1H), 6.35(s, 1H), 5.74(s, 1H), 2.08(s,3H). Elementary analysis Calcd: C 60.15, H 3.82, N 5.69. Found: C 59.85,H 3.86, N 5.66.

[0603]

EXAMPLE 26 Synthesis of a Polymerizable Compound Ir(3-MOI-PPy)(PPy)₂

[0604] As shown in the Reaction Scheme below, 0.37 g (2.38 mmol) of2-methacryloyloxyethyl isocyanate (Trade name “Karenz MOI”, manufacturedby Showa Denko K. K., hereinafter sometimes referred to as “MOI”) wasadded to a solution of 1.34 g (2.0 mmol) of Ir(PPy)₂(3-HO-PPy)synthesized in the same manner as in Example 25, 9 mg of 2,6-di-tert-butyl-4-methylphenol (BHT), and 13 mg of dibutyltin (IV)dilaurate (DBTL) in dry THF under argon stream and the mixture wasallowed to react at 50° C. for 1 hour. Purification of the reactionmixture using a silica gel column followed by distilling off the solventafforded 1.48 g (1.79 mmol) of(2-(3-((2-methacryloyloxyethyl)carbamoyloxy)phenyl)-pyridine)bis(2-phenylpyridine) iridium (III) (Ir(PPy)₂(3-MOI-PPy)).Identification was performed by elementary analysis of C, H and N and¹H-NMR.

[0605]¹H-NMR (CDCl₃, ppm): δ 7.87(d, 2H), 7.80(d, 1H), 7.6(m, 8H),7.42(s, 1H), 6.8(m, 10H), 6.59(d,1H), 6.14 (s, 1H), 5.60(s, 1H),5.21(br, 1H), 4.28(t, 2H), 3.57(m, 2H), 1.96(s, 3H). Elementary analysisCalcd: C 58.17, H 4.03, N 6.78 Found: C 57.78, H 4.02, N 6.72.

[0606]

EXAMPLE 27 Synthesis of a Polymerizable Compound Ir(4-MA-PPy)₂ (PPy)

[0607] (1) 2-(4-Methoxyphenyl)pyridine (4-MeO-PPy) was synthesized by aconventional method.

[0608] That is, as shown in the Reaction Scheme below,(4-methoxyphenyl)magnesium bromide was synthesized from 22.4 g (120mmol) of 4-bromoanisole by a conventional method by using 3.4 g ofmagnesium (Mg) in dry tetrahydrofuran (THF) under argon stream and addedslowly into a solution of 15.8 g (100 mmol) of 2-bromopyridine and 1.8 gof (1,2-bis(diphenylphosphino)-ethane)dichloronickel (II) (Ni(dppe)Cl₂)in dry THF and the mixture was refluxed for 1 hour. After adding 250 mlof an aqueous solution of 5% hydrochloric acid to the reaction mixture,the reaction mixture was washed with chloroform. The water layer wasneutralized with an aqueous solution of sodium hydrogen carbonate andthe objective compound was extracted with chloroform and the organiclayer was distilled off under reduced pressure. The distillateimmediately solidified at room temperature to obtain 15.1 g (81.5 mmol)of 2-(4-methoxy-phenyl)pyridine (4-MeO-PPy) as white solid.Identification was performed by elementary analysis of C, H and N and¹H-NMR.

[0609]¹H-NMR (CDCl₃, ppm): δ 8.65(d, 1H), 7.95(d, 2H), 7.71(t, 1H),7.66(d, 1H), 7.16(t, 1H), 7.00(d, 2H), 3.86(s, 3H). Elementary analysisCalcd: C 77.81, H 5.99, N 7.56. Found: C 77.52, H 6.10, N 7.40.

[0610]

[0611] (2) The methoxy group of 4-MeO-PPy was hydrolyzed by aconventional method.

[0612] That is, as shown in Reaction Scheme below, 15.0 g (80.1 mmol) of4-MeO-PPy was dissolved in concentrated hydrochloric acid and stirred ina sealed vessel at 130° C. for 4 hours. After completion of thereaction, the reaction mixture was neutralized with an aqueous solutionof sodium hydrogen carbonate and the objective compound was extractedwith chloroform. Crystallization of the extract from a chloroform/hexanesolution afforded 10.0 g (58.5 mmol) of 2-(4-hydroxyphenyl)pyridine(4-HO-PPy) as colorless crystal. Identification was performed byelementary analysis of C, H and N, and ¹H-NMR.

[0613]¹H-NMR (CDCl₃, ppm): δ 8.63(d, 1H), 7.82(d, 2H), 7.74(t, 1H),7.65(d, 1H), 7.20(t, 1H), 6.85(d, 2H). Elementary analysis Calcd: C77.17, H 5.30, N 8.18. Found: C 76.91, H 5.39, N 8.02.

[0614]

[0615] (3) 4-HO-PPy was allowed to react with sodium hexachloroiridaten-hydrate (Na₃IrCl₆.nH2O) by a conventional method to synthesizedi(μ-chloro)tetrakis(2-(4-hydroxyphenyl)pyridine) diiridium (III)([Ir(4-HO-PPy)₂Cl]₂).

[0616] That is, as shown in the Reaction Scheme below, 10.0 g ofNa₃IrCl₆.nH₂O was dissolved in 400 ml of a 3:1 mixed solvent of2-ethoxyethanol and water and argon gas was blown therein for 30minutes. Then 8.6 g (5.2 mmol) of 4-HO-PPy was added and dissolved inthe solution under argon stream, followed by reflux for 5 hours. Aftercompletion of the reaction, the solvent was distilled off andrecrystallization of the residue from ethanol afforded 5.88 g (5.18mmol) of [Ir(4-HO-PPy)₂Cl]₂ as reddish brown crystal. Identification wasperformed by elementary analysis of C, H and N and ¹H-NMR.

[0617]¹H-NMR (DMSO-d₆, ppm): δ 9.66(d, 2H), 9.38(d, 2H), 7.95(m, 8H),7.61(d, 2H), 7.54(d, 2H), 7.38(t, 2H), 7.26(t, 2H), 6.33(d, 2H), 6.28(d,2H), 5.67(s, 2H), 5.12(s, 2H). Elementary analysis Calcd: C 46.52, H2.84, N 4.93. Found: C 46.33, H 2.51, N 4.76.

[0618]

[0619] (4) [Ir(4-HO-PPy)₂Cl]₂ was allowed to react with 2-phenylpyridine(PPy) in the presence of silver (I) trifluoromethanesulfonate (AgCF₃SO₃)by a conventional method.

[0620] That is, as shown in the Reaction Scheme below, 1.98 g ofAgCF₃SO₃ was added to a suspension of 3.98 g (3.5 mmol) of[Ir(4-HO-PPy)₂Cl]₂ and 15.5 g (10.0 mmol) of PPy in dry toluene and themixture was refluxed for 6 hours. Purification of the reaction mixtureusing a silica gel column followed by distilling off the solventafforded 2.20 g (3.2 mmol) ofbis(2-(4-hydroxyphenyl)pyridine)(2-phenylpyridine)iridium (III)(Ir(4-HO-PPy)₂(PPy)) as yellow powder. Identification was performed byelementary analysis of C, H and N and ¹H-NMR.

[0621]¹H-NMR (CDCl₃, ppm): δ 7.88(d, 1H), 7.78(d, 2H), 7.6(m, 9H),6.85(m, 8H), 6.64(d, 2H). Elementary analysis Calcd: C 57.71, H 3.52, N6.12. Found: C 57.46, H 3.49, N 5.99.

[0622]

[0623] (5) As shown in the Reaction Scheme below, 0.50 g (4.8 mmol) ofmethacryloyl chloride was added to a solution of 1.37 g (2.0 mmol) ofIr(4-HO-PPy)₂(PPy) and 0.81 g (8.0 mmol) of triethylamine as a base indry THF under argon stream and the mixture was allowed to react at 20°C. for 5 hours. Triethylamine hydrochloride was filtered off from thereaction mixture and purification of the filtrate using a silica gelcolumn followed by distilling of the solvent afforded 1.55 g (1.88 mmol)of bis(2-(4-methacryloyloxyphenyl)pyridine) (2-phenylpyridine) iridium(III) (Ir(4-MA-PPy)₂(PPy)). Identification was performed by elementaryanalysis of C, H and N and ¹H-NMR.

[0624]¹H-NMR (CDCl₃, ppm): δ 7.87(d, 1H), 7.78(d, 2H), 7.6(m, 9H),6.8(m, 8H), 6.59(s ,2H), 6.35(s, 2H), 5.74(s, 2H), 2.08(s, 6H).Elementary analysis Calcd: C 59.84, H 3.92, N 5.11. Found: C 59.95, H3.82, N 5.04.

[0625]

EXAMPLE 28 Synthesis of a Polymerizable Compound Ir(4-MOI-PPy)₂ (PPy)

[0626] As shown in the Reaction Scheme below, 0.75 g (4.83 mmol) of2-methacryloyloxyethyl isocyanate (Trade name “Karenz MOI”, manufacturedby Showa Denko K. K., hereinafter sometimes referred to as “MOI”) wasadded to a solution of 1.37 g (2.0 mmol) of Ir(4-HO-PPy)₂(PPy)synthesized in the same manner as in Example 27, 18 mg of2,6-di-tert-butyl-4-methylphenol (BHT), and 26 mg of dibutyltin (IV)dilaurate (DBTL) in dry THF under argon stream and the mixture wasallowed to react at 50° C. for 1 hour. Purification of the reactionmixture using a silica gel column followed by distilling off the solventafforded 1.68 g (1.68 mmol) of bis(2-(4-((2-methacryloyloxyethyl)carbamoyloxy)phenyl)-pyridine)(2-phenylpyridine)iridium (III) (Ir(4-MOI-PPy)₂(PPy)). Identificationwas performed by elementary analysis of C, H and N and ¹H-NMR.

[0627]¹H-NMR (CDCl₃, ppm): δ 7.85(d, 1H), 7.81 (d, 2H), 7.6(m, 9H), 6.8(m, 8H), 6.58 (d, 2H), 6.12 (s, 2H), 5.60 (s, 2H), 5.21 (br, 2H),4.28(t, 4H), 3.58(m, 4H), 1.96 (s, 6H). Elementary analysis Calcd: C56.62, H 4.25, N 7.02. Found: C 56.38, H 4.02, N 6.72.

[0628]

EXAMPLE 29 Synthesis of Ir(3-MA-PPy)(PPy)₂ Polymer

[0629] In a reactor were charged 1.11 g (1.5 mmol) of Ir(3-MA-PPy)(PPy)₂complex synthesized in Example 25, 0.010 g (0.061 mmol) of2,2′-azobis(isobutyronitrile) (AIBN), and 10 ml of butyl acetate and theatmosphere was exchanged with nitrogen. Thereafter, the mixture wasallowed to react at 80° C. for 10 hours (cf. Reaction Scheme below).After completion of the reaction, the reaction mixture was dripped intoacetone to perform reprecipitation and the resultant polymer wasrecovered by filtration. A procedure of reprecipitation by dripping achloroform solution of the recovered polymer into methanol was furtherrepeated 2 times to purify the polymer, which was then recovered anddried in vacuum to afford 0.92 g of the objective Ir(3-MA-PPy)(PPy)₂polymer as powder. The elementary analysis of C, H, N of the obtainedpolymer indicated that the polymer had the same composition asIr(3-MA-PPy)(PPy)₂. The weight average molecular weight of the polymerwas 12,000 in terms of polystyrene (GPC measurement, eluent: THF).

EXAMPLE 30 Synthesis of Ir(3-MOI—PPy)(PPy)₂ polymer

[0630] In a reactor were charged 1.11 g (1.5 mmol) ofIr(3-MOI—PPy)(PPy)₂ complex synthesized in Example 26, 0.010 g (0.061mmol) of 2,2′-azobis(isobutyronitrile)(AIBN), and 10 ml of butyl acetateand the atmosphere was exchanged with nitrogen. Thereafter, the mixturewas allowed to react at 80° C. for 10 hours (cf. Reaction Scheme below).After completion of the reaction, the reaction mixture was dripped intoacetone to perform reprecipitation and the resultant polymer wasrecovered by filtration. A procedure of reprecipitation by dripping achloroform solution of the recovered polymer into methanol was furtherrepeated 2 times to purify the polymer, which was then recovered anddried in vacuum to afford 1.02 g of the objective Ir(3-MOI—PPy)(PPy)₂polymer as powder. The elementary analysis of C, H, N and Ir of theobtained polymer indicated that the polymer had substantially the samecomposition as Ir(3-MOI—PPy)(PPy)₂ The weight average molecular weightof the polymer was 20,000 in terms of polystyrene (GPC measurement,eluent:THF).

EXAMPLE 31 Synthesis of Ir(3-MA-PPy)(3-PrCO—PPy)₂ polymer

[0631] In a reactor were charged 2.22 g (2.5 mmol) of Ir(3-MA-PPy)(3-PrCO—PPy)₂ complex synthesized in Example 1, 0.010 g (0.061 mmol) of2,2′-azobis(isobutyronitrile)(AIBN), and 30 ml of butyl acetate and theatmosphere was exchanged with nitrogen. Thereafter, the mixture wasallowed to react at 80° C. for 10 hours (cf. Reaction Scheme below).After completion of the reaction, the reaction mixture was dripped intoacetone to perform reprecipitation and the resultant polymer wasrecovered by filtration. A procedure of reprecipitation by dripping achloroform solution of the recovered polymer into methanol was furtherrepeated 2 times to purify the polymer, which was then recovered anddried in vacuum to afford 1.85 g of the objectiveIr(3-MA-PPy)(3-PrCO—PPy)₂ polymer as powder. The elementary analysis ofC, H, N of the obtained polymer indicated that the polymer had the samecomposition as Ir(3-MA-PPy)(3-PrCO—PPy)₂. The weight average molecularweight of the polymer was 8,000 in terms of polystyrene (GPCmeasurement, eluent:THF).

EXAMPLE 32 Synthesis of Ir(3-MA-PPy)₃ Polymer

[0632] In a reactor were charged 2.28 g (2.5 mmol) of the Ir(3-MA-PPy)₃complex synthesized in Example 12, 0.010 g (0.061 mmol) of 2,2′-azobis(isobutyronitrile)(AIBN), and 30 ml of butyl acetate and the atmospherewas exchanged with nitrogen. Thereafter, the mixture was allowed toreact at 80° C. for 10 hours (cf. Reaction Scheme below). As a result aninsoluble polymer precipitated. The polymer was recovered by filtration,washed with 100 ml of chloroform and then with 100 ml of methanol, anddried under vacuum to obtain 2.10 g of the objective Ir(3-MA-PPy)₃polymer as powder. Elementary analysis of C, H and N of the obtainedpolymer supported for its having substantially identical compositionwith that of Ir(3-MA-PPy)₃. The polymer was deemed to have a crosslinkedstructure and was insoluble in most of common organic solvents so thatit was impossible to measure its molecular weight by GPC.

EXAMPLE 33 Synthesis of Ir(3-MOI—PPy)(3-PrCO—PPy)₂ Polymer

[0633] In a reactor were charged 2.43 g (2.5 mmol) ofIr(3-MOI—PPy)(3-PrCO—PPy)₂ complex synthesized in Example 3, 0.010 g(0.061 mmol) of 2,2′-azobis (isobutyronitrile) (AIBN), and 30 ml ofbutyl acetate and the atmosphere was exchanged with nitrogen.Thereafter, the mixture was allowed to react at 80° C. for 10 hours (cf.Reaction Scheme below). After completion of the reaction, the reactionmixture was dripped into acetone to perform reprecipitation and theresultant polymer was recovered by filtration. A procedure ofreprecipitation by dripping a chloroform solution of the recoveredpolymer into methanol was further repeated 2 times to purify thepolymer, which was then recovered and dried in vacuum to afford 2.05 gof the objective Ir(3-MOI—PPy)(3-PrCO—PPy)₂ polymer as powder. Theelementary analysis of C, H, N of the obtained polymer supported for itshaving substantially the same composition as that of Ir(3-MOI-PPy)(3-PrCO—PPy)₂. The weight average molecular weight of the polymer was18,000 in terms of polystyrene (GPC measurement, eluent:THF).

EXAMPLE 34 Synthesis of Ir(3-MOI—PPy)₂(3-PrCO—PPy) Polymer

[0634] In a reactor were charged 2.46 g (2.5 mmol) ofIr(3-MOI—PPy)₂(3-PrCO—PPy) complex synthesized in Example 13, 0.010 g(0.061 mmol) of 2,2′-azobis(isobutyronitrile) (AIBN), and 30 ml of butylacetate and the atmosphere was exchanged with nitrogen. Thereafter, themixture was allowed to react at 80° C. for 10 hours (cf. Reaction Schemebelow). As a result an insoluble polymer precipitated. The polymer wasrecovered by filtration, washed with 100 ml of chloroform and then with100 ml of methanol, and dried under vacuum to obtain 2.21 g of theobjective Ir(3-MOI—PPy)₂ (3-PrCO—PPy) polymer as powder. Elementaryanalysis of C, H and N of the obtained polymer supported for its havingsubstantially the same composition as that of Ir(3-MOI-PPy)₂(3-PrCO—PPy). The polymer was deemed to have a crosslinked structure andwas insoluble in most of common organic solvents so that it wasimpossible to measure its molecular weight by GPC.

EXAMPLE 35 Synthesis of Ir(3-MA-PPy)(3-PrCO—PPy)₂/Ir(3-MA-PPy)₃Copolymer

[0635] In a reactor were charged 1.11 g (1.25 mmol) of Ir(3-MA-PPy)(3-PrCO—PPY)₂ complex synthesized in Example 1, 1.14 g (1.25 mmol) ofIr(3-MA-PPy)₃ complex synthesized in Example 12, 0.010 g (0.061 mmol) of2,2′-azobis(isobutyronitrile) (AIBN), and 30 ml of butyl acetate and theatmosphere was exchanged with nitrogen. Thereafter, the mixture wasallowed to react at 80° C. for 10 hours (cf. Reaction Scheme below). Asa result an insoluble polymer precipitated. The polymer was recovered byfiltration, washed with 100 ml of chloroform and then with 100 ml ofmethanol, and dried under vacuum to obtain 2.05 g of the objectiveIr(3-MA-PPy)(3-PrCO—PPy)₂/Ir(3-MA-PPy)₃ copolymer as powder. Elementaryanalysis of C, H and N of the obtained copolymer supported for thepolymerization of Ir(3-MA-PPy)(3-PrCo—PPy)₂ with Ir(3-MA-PPy)₃ in amolar ratio of 1:1. The copolymer was deemed to have a crosslinkedstructure and was insoluble in most of common organic solvents so thatit was impossible to measure its molecular weight by GPC.

EXAMPLE 36 Synthesis of Ir(3-MOI—PPy)(3-PrCO—PPy)₂/Ir(3-MOI—PPy)₂(3-PrCO—PPy) Copolymer

[0636] In a reactor were charged 1.21 g (1.25 mmol) ofIr(3-MOI—PPy)(3-PrCO—PPy)₂ complex synthesized in Example 3, 1.23 g(1.25 mmol) of Ir(3-MOI—PPy)₂ (3-PrCO—PPy) complex synthesized inExample 13, 0.010 g (0.061 mmol) of 2,2′-azobis(isobutyro-nitrile)(AIBN), and 30 ml of butyl acetate and the atmosphere was exchanged withnitrogen. Thereafter, the mixture was allowed to react at 80° C. for 10hours (cf. Reaction Scheme below). As a result an insoluble polymerprecipitated. The polymer was recovered by filtration, washed with 100ml of chloroform and then with 100 ml of methanol, and dried undervacuum to obtain 2.18 g of the objectiveIr(3-MOI—PPy)(3-PrCO—PPy)₂/Ir(3-MOI-PPy)₂ (3-PrCO—PPy) copolymer aspowder. Elementary analysis of C, H and N of the obtained copolymersupported for the polymerization of Ir(3-MOI—PPy)(3-PrCO—PPy)₂ withIr(3-MOI-PPy)₂ (3-PrCO—PPy) in a molar ratio of 1:1. The copolymer wasdeemed to have a crosslinked structure and was insoluble in most ofcommon organic solvents so that it was impossible to measure itsmolecular weight by GPC.

EXAMPLE 37 Synthesis of a Polymerizable Compound(8-nonen-2,4-dionato)bis(2-phenylpyridine)Iridium (III) (HereinafterAbbreviated as Ir(PPy)₂ (1-Bu-acac))

[0637] As shown in the Reaction Scheme below,di(μ-chloro)tetrakis(2-phenylpyridine)diiridium (III) (hereinafterabbreviated as [Ir(PPy)₂Cl]₂) synthesized by a conventional method and8-nonen-2,4-dione synthesized by the known method (H. Gerlach et al.,Helv. Chim. Acta, 60, 638 (1977)) were allowed to react to synthesizeIr(PPy)₂ (1-Bu-acac).

[0638] That is, 261 mg (0.24 mmol) of [Ir(PPy)₂Cl]₂ was suspended in 30ml of nitrogen-purged methanol and 87 mg (0.56 mmol) of8-nonen-2,4-dione and 76 mg (0.75 mmol) of triethylamine were addedthereto, and the obtained mixture was heated under reflux in an oil bathfor 3 hours. The obtained pale yellow reaction mixture was cooled toroom temperature and concentrated by using a rotary evaporator. Then,200 ml of dilute hydrochloric acid solution and 50 ml of chloroform wereadded to the reaction mixture and the obtained mixture was stirredvigorously. The chloroform layer was separated and dried over magnesiumsulfate and the solvent was distilled off under reduced pressure. Theobtained yellow residue was dissolved in dichloromethane and thesolution was subjected to silica gel column chromatography to separate apale yellow main product. A solution of the product was concentratedunder reduced pressure and then a small amount of hexane was addedthereto, followed by cooling to −20° C. to obtain 270 mg (0.41 mmol) ofthe objective Ir(PPy)₂(1-Bu-acac) as pale yellow crystal (yield: 85%).Identification was performed by elementary analysis of C, H and N and¹H-NMR.

[0639]¹H-NMR (CDCl₃, ppm): δ 8.49 (d, J=5.7 Hz, 2H, PPy), 7.83 (t, J=7.8Hz, 2H, PPy), 7.70 (m, 2H, PPy), 7.54 (t, J=6.8 Hz, 2H, PPy), 7.10 (m,2H, PPy), 6.80 (t, J=7.3 Hz, 2H, PPy), 6.68 (m, 2H, PPy), 6.35 (d, J=6.2Hz, 1H, PPy), 6.25 (d, J=6.2 Hz, 1H, PPy), 5.61 (m, 1H, —CH═CH₂), 5.19(s, 1H, diketonate-methine), 4.86 (m, 2H, —CH═CH₂), 1.99 (t, J=7.3 Hz,2H, methylene), 1.79 (s, 3H, CH₃), 1.72 (m, 2H, methylene), 1.38 (m, 2H,methylene). Elementary Calcd: C 56.95; H 4.47, N 4.28. (C₃₁H₂₉IrN₂O₂)analysis Found: C 55.84, H 4.32, N 3.97.

[0640]

EXAMPLE 38 Synthesis of a Polymerizable Compound[6-(4-vinylphenyl)-2,4-hexanedionato]bis(2-phenylpyridine)iridium (III)(Hereinafter Abbreviated as Ir(PPy)₂[1-(St-Me)-acac])

[0641] (1) As shown in the Reaction Scheme below, acetylacetone and4-vinylbenzyl chloride were allowed to react to synthesize6-(4-vinylphenyl)-2,4-hexanedione

[0642] That is, 1.23 g (60% in oil) (31 mmol) of sodium hydride wasweighed in a nitrogen atmosphere and 60 ml of dry tetrahydrofuran(hereinafter abbreviated as THF) was added thereto and the mixture wascooled to 0° C. in an ice bath. To the suspension was dripped a mixedsolution of 2.5 g (24 mmol) of acetylacetone and 1 ml of hexamethylphosphoric triamide to produce colorless precipitate. After stirring themixture at 0° C. for 10 minutes, 17.5 ml (28 mmol) of a hexane solution(1.6 M) of n-butyllithium was dripped therein to dissolve theprecipitate and the mixture was further stirred at 0° C. for 20 minutes.To the obtained pale yellow solution was dripped 4.0 g (26 mmol) of4-vinylbenzyl chloride and the reaction mixture was warmed back to roomtemperature and stirred for 20 minutes. Then, dilute hydrochloric acidwas added thereto to render the water layer acidic. The organic layerwas washed with saturated sodium chloride solution and dried overmagnesium sulfate, and the solvent was distilled off by using a rotaryevaporator. The obtained reaction mixture was charged in a silica gelcolumn and developed with a mixed solvent of hexane/dichloromethane (1:1(by volume)) to separate a main product. Distilling off the solvent fromthe obtained solution afforded 3.0 g (14 mmol) of the objective6-(4-vinylphenyl)-2,4-hexanedione as a brown liquid. Yield was 56%.Identification was performed by elementary analysis of C and H, and¹H-NMR.

[0643]¹H-NMR (CDCl₃, ppm): enol; δ 7.33 (d, J=8.1 Hz, 2H, aromatic),7.14 (d, J=8.4 Hz, 2H, aromatic), 6.68 (dd, J=8.1 Hz, 1H, vinylic), 5.70(d, J=17.0 Hz, 1H, vinylic), 5.46 (s, 1H, diketonate-methine), 5.20 (d,J=11.1 Hz, 1H, vinylic), 2.91 (t, J=5.7 Hz, 2H, methylene), 2.58 (t,J=7.3 Hz, 2H, methylene), 2.03 (s, 3H, methyl). keto; δ 7.33 (d, J=8.1Hz, 2H, aromatic), 7.14 (d, J=8.4 Hz, 2H, aromatic), 6.68 (dd, J=8.1 Hz,1H, vinylic), 5.70 (d, J=17.0 Hz, 1H, vinylic), 5.20 (d, J=11.1 Hz, 1H,vinylic), 3.53 (s, 2H, C(═O)CH₂C(═O)), 2.89 (m, 4H, ethylene), 2.19 (s,3H, methyl). enol:keto=6:1. Elementary analysis Calcd: C 77.75, H 7.46.(C₁₄H₉O₂) Found: C 77.49, H 7.52.

[0644]

[0645] (2) As shown in the Reaction Scheme below,6-(4-vinylphenyl)-2,4-hexanedione thus obtained and [Ir(PPy)₂Cl]₂synthesized by a conventional method were allowed to react to synthesizeIr(PPy)₂[1-(St-Me)-acac].

[0646] That is, to a solution of 342 mg (0.32 mmol) of [Ir(PPy)₂Cl]₂,158 mg (1.5 mmol) of sodium carbonate and 5 mg (0.023 mmol) of2,6-di-tert-butyl-4-methylphenol in 5 ml of N,N-dimethylformamide(hereinafter, abbreviated as DMF) was added210 mg (0.97 mmol) of6-(4-vinylphenyl)-2,4-hexanedione and the mixture was heated at 65° C.with stirring. Then, the reaction mixture was cooled to room temperatureand dilute hydrochloric acid solution was added thereto, followed byextracting a component having a pale yellow color with chloroform. Afterdistilling off the solvent by using a rotary evaporator, the residue wasdissolved in a small amount of dichloromethane and subjected to silicagel column chromatography (eluent:dichloromethane) to separate a yellowmain product. The solution was concentrated to dryness under reducedpressure and dichloromethane/hexane mixed solvent was added to theresidue to perform recrystallization at −20° C., which afforded 354 mg(0.49 mmol) of the objective Ir(PPy)₂[1-(St-Me)-acac] as pale yellowcrystal. Yield: 78%. Identification was performed by elementary analysisof C, H and N and ¹H-NMR.

[0647]¹H-NMR (CDCl₃, ppm): δ 8.47 (d, J=5.7 Hz, 1H, PPy), 8.21 (d, J=5.7Hz, 1H, PPy), 7.9-7.5 (m, 6H, PPy), 7.18 (d, J=8.1 Hz, 2H,stylyl-aromatic), 7.00 (m, 2H, PPy), 6.89 (d, J=8.1 Hz, 2H,stylyl-aromatic), 6.75 (m, 5H, PPy and vinylic), 6.28 (t, J=7.3 Hz, 2H,PPy), 7.67 (d, J=17.6 Hz, 1H, vinylic), 5.19 (d, J=9.5 Hz, 1H, vinylic),5.17 (s, 1H, diketonate-methine), 2.60 (t, J=7.3 Hz, 2H, ethylene), 2.36(m, 2H, ethylene), 1.75 (s, 3H, methyl). Elementary Calcd: C 60.40, H4.36, N 3.91. (C₃₆H₃₁IrN₂O₂) analysis Found: C 61.35, H 4.34, N 3.83.

[0648]

EXAMPLE 39 Synthesis of a Polymerizable Compound(9-acryloyloxy-2,4-nonanedionato)bis(2-phenylpyridine)iridium (III)(Hereinafter Abbreviated as Ir(PPy)₂[1-(A-Bu)-acac])

[0649] (1) As shown in the Reaction Scheme below,(9-hydroxy-2,4-nonanedionato)bis(2-phenylpyridine)iridium (III)(hereinafter abbreviated as Ir(PPy)₂[1-(OH-Bu)-acac]) was synthesized bya conventional method.

[0650] That is, to a solution of 167 mg (0.276 mmol) ofIr(PPy)₂(1-Bu-acac) synthesized in the same manner as in Example 37 in10 ml of THF was dripped 1.0 ml (0.5 mmol) of 0.5M THF solution of9-borabicyclo[3.3.1]nonane (hereinafter abbreviated as 9-BBN) and thesolution was heated under reflux for 25 minutes. Then, to the reactionmixture were added 0.2 ml (0.60 mmol) of a 3M aqueous NaOH solution and0.060 ml (0.62 mmol) of a 35% H₂O₂ solution in the order cited, and themixture was stirred at room temperature for 12 hours. Then, 20 ml ofwater was added thereto and the mixture was concentrated by using arotary evaporator. After adding chloroform and well shaking, the organiclayer was concentrated to dryness under reduced pressure. The obtainedyellow solid was dissolved in a small amount of dichloromethane and thesolution was charged in a silica gel column followed by flowingdichloromethane therethrough to remove eluted impurities. Subsequently,flowing a dichloromethane/ethyl acetate mixed solvent of 1:1 (by volumeratio) resulted in elution of a pale yellow complex, which was recoveredand dried under reduced pressure, followed by recrystallization of theresidue from dichloromethane/hexane mixed solution at −20° C. to obtain23 mg (0.034 mmol) of Ir(PPy)₂[1-(OH-Bu)-acac) as pale yellow solid.Yield: 13%. Identification was performed by elementary analysis of C, Hand N and ¹H-NMR.

[0651]¹H-NMR (CDCl₃, ppm): δ 8.50 (d, J=5.9 Hz, 2H, PPy), 7. 82 (t,J=7.0 Hz, 2H, PPy), 7.72 (t, J=7.3 Hz, 2H, PPy), 7.55 (t, J=7.0 Hz, 2H,PPy), 7.12 (t, J=5.9 Hz, 2H, PPy), 6.81 (t, J=7.6 Hz, 2H, PPy), 6.69 (t,J=7.3 Hz, 2H, PPy), 6.31 (d, J=5.9 Hz, 1H, PPy), 6.26 (d, J=5.9 Hz, 1H,PPy), 5.19 (s, 1H, diketonate-methine), 3.44 (t, J=7.0 Hz, 2H, CH₂OH),1.98 (t, J=7.0 Hz, 2H, methylene), 1.79 (s, 3H, methyl), 1.34 (m, 4H,methylene), 1.05 (m, 2H, methylene). Elementary Calcd: C 55.42, H 4.65,N 4.17. (C₃₁H₃₁IrN₂O₃) analysis Found: C 55.76, H 4.71, N 4.19.

[0652]

[0653] (2) As shown in the Reaction Scheme below,Ir(PPy)₂[1-(OH-Bu)-acac] and acryloyl chloride were allowed to react tosynthesize Ir(PPy)₂[1-(A-Bu)-acac].

[0654] That is, to a solution of 95 mg (0.14 mmol) ofIr(PPy)₂[1-(OH-Bu)-acac] in 10 ml of dichloromethane was added 0.10 ml(0.72 mmol) of triethylamine. To this solution was added 0.060 ml (0.74mmol) of acryloyl chloride and the mixture was stirred at roomtemperature for 30 minutes. Then, after adding 1 ml of methanol to themixture, the solvent was distilled under reduced pressure and theresidue was passed through a silica gel column (eluent:dichloromethane)and an initially eluted yellow solution was separated and concentratedto dryness under reduced pressure. Recrystallization of the residue fromdichloromethane/hexane mixed solvent at −20° C. afforded 99 mg (0.14mmol) of the objective Ir(PPy)₂[1-(A-Bu)-acac] as pale yellow solid.Yield: 96%. Identification was performed by elementary analysis of C, Hand N and ¹H-NMR.

[0655]¹H-NMR (CDCl₃, ppm): δ 8.50 (d, J=5.9 Hz, 2H, PPy), 7.80 (m, 4H,PPy), 7.51 (t, J=7.3 Hz, 2H, PPy), 7.18 (t, J=5.9 Hz, 2H, PPy), 6.84 (t,J=7.3 Hz, 2H, PPy), 6.70 (t, J=7.6 Hz, 2H, PPy), 6.25 (m, 3H,PPy+vinylic), 6.12 (dd, J=15.6, 9.3 Hz, 1H, vinylic), 5.75 (d, J=9.3 Hz,1H, vinylic), 5.17 (s, 1H, diketonate-methine), 4.05 (t, J=7.0 Hz, 2H,—COOCH₂—), 1.84 (t, J=7.0 Hz, 2H, methylene), 1.80 (s, 3H, methyl), 1.34(m, 4H, methylene), 1.06 (m, 2H, methylene). Elementary Calcd: C 56.26,H 4.58, N 3.86. (C₃₄H₃₃IrN₂O₄) analysis Found: C 56.55, H 4.53, N 3.60.

[0656]

EXAMPLE 40 Synthesis of a Polymerizable Compound{1-[4-(2-methacryloyloxy)ethylcarbamoyloxyphenyl]-3-phenyl-1,3-propane-dionato]bis(2-phenylpyridine)iridium(III) (hereinafter abbreviated as Ir(PPy)₂(MOI-Ph-acac))

[0657] (1) As shown in the Reaction Scheme below,di(1-chloro)-tetrakis(2-phenylpyridine)diiridium (III) ((Ir(PPy)₂Cl]₂)synthesized by a conventional method and p-hydroxy-dibenzoylmethanesynthesized by referencing the known method (M. Cushman et al.,Tetrahedron Lett., 31, 6497 (1990)) were allowed to react to synthesize[1-(4-hydroxyphenyl)-3-phenyl-1,3-propane-dionato]bis(2-phenylpyridine)iridium(III) (hereinafter abbreviated as Ir(PPy)₂(OH-Ph-acac)).

[0658] That is, 112 mg (0.10 mmol) of [Ir(PPy)₂Cl]₂, 64 mg (0.60 mmol)of sodium carbonate and 76 mg (0.32 mmol), of p-hydroxydibenzoylmethanewere dissolved in 10 ml of DMF and the solution was heated at 60° C. for0.5 hour with stirring. The obtained reaction mixture was poured into100 ml of dilute hydrochloric acid solution and the iridium complex wasextracted with chloroform. The chloroform was distilled off by using arotary evaporator and the residue was dissolved in a small amount ofdichloromethane and charged in a silica gel column. Development with amixed solvent of dichloromethane/acetone of 30:10 (by volume ratio)resulted in elution of a component having an orange color, which wasrecovered and concentrated to dryness under reduced pressure. Theobtained solid was dissolved in a small amount of diethyl ether andhexane was added thereto. The precipitate was collected by filtrationand dried under reduced pressure to obtain 111 mg (0.15 mmol) of theobjective Ir(PPy)₂(OH-Ph-acac) as orange solid. Yield: 72%.Identification was performed by elementary analysis of C, H and N and¹H-NMR.

[0659]¹H-NMR (CDCl₃, ppm): δ 8.58 (d, 2H, PPy), 7.9-6.7 (m, 21H,PPy+phenyl), 6.52 (s, 1H, diketonate-methine), 6.37 (d, 2 H!, PPy), 4.91(s, 1H, OH). Elementary Calcd: C 60.07, H 3.68, N 3.79. (C₃₇H₂₇IrN₂O₃)analysis Found: C 60.77, H 3.75, N 3.62.

[0660]

[0661] (2) As shown in the Reaction Scheme below, the obtainedIr(PPy)₂(OH-Ph-acac) and 2-methacryloyloxyethyl isocyanate (Trade name“Karenz MOI”, manufactured by Showa Denko K. K., hereinafter sometimesreferred to as “MOI”) were allowed to react to synthesizeIr(PPy)₂(MOI-Ph-acac).

[0662] That is, to a solution of 110 mg (0.15 mmol) ofIr(PPy)₂(OH-Ph-acac) in 50 ml of toluene were added 5 mg (0.023 mmol) of2,6-di-tert-butyl-4-methylphenol (hereinafter abbreviated as BHT), 32 mg(0.051 mmol) of dibutyltin (IV) dilaurate (hereinafter abbreviated asDBTL) and 121 mg (0.78 mmol) of MOI and the mixture was heated at 70° C.for 6 hours with stirring. The obtained reaction mixture was air-cooledto room temperature and charged in a silica gel column, followed bydevelopment of the column with a mixed solvent ofdichloromethane/acetone of 20:1 (by volume ratio), resulting in elutionof an orange-colored compound. The solution containing the compound wasconcentrated to dryness under reduced pressure by using a rotaryevaporator and the obtained solid was dissolved in a small amount ofdichloromethane. Slowly adding hexane to the dichloromethane solutionresulted in deposition of an orange-colored precipitate, which wascollected by filtration and dried under reduced pressure to obtain 100mg (0.11 mmol) of the objective Ir(PPy)₂(MOI-Ph-acac) as orange-coloredsolid. Yield: 75%. Identification was performed by elementary analysisof C, H and N and ¹H-NMR.

[0663]¹H-NMR (CDCl₃, ppm): δ 8.60 (d, 2H, PPy), 7.9-6.7 (m, 21H, PPy andphenyl), 6.56 (s, 1H, diketonate-methine), 6.39 (d, 2H, PPy), 6.18 (s,1H, olefinic), 5.65 (s, 1H, olefinic), 5.29 (s, 1H, NH), 4.31 (t, 2H,ethylene), 3.59 (t, 2H, ethylene), 2.00 (s, 3H, methyl). ElementaryCalcd: C 59.05, H 4.05, N 4.70. (C₄₄H₃₆IrN₃O₆) analysis Found: C 59.79,H 4.05, N 4.64.

[0664]

EXAMPLE 41 Synthesis of a Polymerizable Compound[6-(4-methacryloyloxyphenyl)-2,4-hexanedionato]bis(2-phenylpyridine)iridium(III) (hereinafter abbreviated as Ir(PPy)₂[1-(MA-Ph-Me)-acac)

[0665] (1) As shown in the Reaction Scheme below, acetylacetone and4-benzyloxybenzyl iodide synthesized by the known method (C. Cativiela,et al., J. Org. Chem., 60, 3074 (1995)) were allowed to react tosynthesize 6-(4-benzyloxyphenyl)-2,4-hexanedione.

[0666] That is, 0.30 g (60% in oil) (7.5 mmol) of sodium hydride wasweighed in a nitrogen atmosphere and 20 ml of THF was added thereto andthe mixture was cooled to 0° C. in an ice bath. To the suspension wasdripped a mixed solution of 0.75 g (7.5 mmol) of acetylacetone and 0.5ml of hexamethyl phosphoric triamide to produce colorless precipitate.After stirring the mixture at 0° C. for 10 minutes, 4.6 ml (7.5 mmol) ofa hexane solution (1.6 M) of n-butyllithium was dripped therein todissolve the precipitate and the mixture was further stirred at 0° C.for 20 minutes. To the obtained pale yellow transparent solution wasdripped a solution of 2.28 g (7.0 mmol) of 4-benzyloxybenzyl iodide in10 ml of THF. After stirring the reaction mixture at room temperaturefor 1 hour, it was cooled again to 0° C. Then, dilute hydrochloric acidwas added thereto to neutralize it. After washing the organic layer witha saturated aqueous solution of sodium chloride, the solvent wasdistilled off by using a rotary evaporator. The residue was passedthrough a-silica gel column (eluent: a mixed solvent ofdichloromethane/hexane of 1:1 (by volume ratio)) to separate a mainproduct. Separation of this and concentration to dryness under reducedpressure afforded 1.31 g (4.4 mmol) of the objective6-(4-benzyloxyphenyl)-2,4-hexanedione as pale yellow solid. Yield: 63%.Identification was performed by elementary analysis of C and H, and¹H-NMR.

[0667]¹H-NMR (CDCl₃, ppm): enol: δ 7.5-6.8 (m, 9H, aromatic), 5.46 (s,1H, enol-methine), 5.04 (s, 2H, —O—CH₂—), 2.88 (t, J=7.6 Hz, 2H,ethylene), 2.55 (t, J=8.4 Hz, 2H, ethylene), 2.04 (s, 3H, methyl). keto;δ 7.5-6.8 (m, 9H, aromatic), 5.04 (s, 2H, —O—CH₂—), 3.53 (s, 2H,C(═O)CH₂C(═O)), 2.84 (m, 4H, ethylene), 2.19 (s, 3H, methyl).enol:keto=5:1. Elementary analysis Calcd: C 77.00, H 6.86. (C₁₉H₂₀O₃)Found: C 77.46, H 6.77.

[0668]

[0669] (2) As shown in the Reaction Scheme below, the obtained6-(4-benzyloxyphenyl)-2,4-hexanedione was hydrogenated to produce6-(4-hydroxyphenyl)-2,4-hexanedione.

[0670] That is, 1.5 g of Pd-activated carbon (10%) was weighed in anitrogen atmosphere and 20 ml of dichloromethane and 1.31 g (4.4 mmol)of 6-(4-benzyloxyphenyl)-2,4-hexanedione were added thereto. Theatmosphere in the reaction system was exchanged with hydrogen at 1 atmand stirred at room temperature for 11 hours. The obtained reactionmixture was filtered to remove insoluble matter and the solvent wasdistilled off under reduced pressure. The residue was charged in asilica gel column and developed first with dichloromethane to removebyproducts. Subsequently, a solution containing a compound eluted fromthe column with a mixed solvent of 1:1 (by volume ratio) acetone/hexanewas concentrated to dryness under reduced pressure to obtain 0.70 g (3.4mmol) of the objective 6-(4-hydroxyphenyl)-2,4-hexanedione as paleyellow solid. Yield: 77%. Identification was performed by elementaryanalysis of C and H, and ¹H-NMR.

[0671]¹H-NMR (CDCl₃, ppm): enol: δ 7.04 (d, J=8.4 Hz, 2H, aromatic),6.65 (d, J=8.4 Hz, 2H, aromatic), 5.55 (br, 1H, OH), 5.47 (s, 1H,enol-methine), 2.86 (t, J=7.3 Hz, 2H, ethylene), 2.55 (t, J=7.3 Hz, 2H,ethylene), 2.04 (s, 3H, methyl). keto: δ 7.04 (d, J=8.4 Hz, 2H,aromatic), 6.65 (d, J=8.4 Hz, 2H, aromatic), 5.55 (br, 1H, OH), 3.55 (s,2H, C(═O)CH₂C(═O)), 2.83 (m, 4H, ethylene), 2.19 (s, 3H, methyl).enol:keto=5:1. Elementary analysis Calcd: C 69.88, H 6.84. (C₁₂H₁₄O₃)Found: C 69.67, H 6.79.

[0672]

[0673] (3) As shown in the Reaction Scheme below, the obtained6-(4-hydroxyphenyl)-2,4-hexanedione was allowed to react withdi(μ-chloro)tetrakis(2-phenylpyridine)diiridium (III) ([Ir(PPy)₂Cl]₂)synthesized by a conventional method to synthesize[6-(4-hydroxyphenyl)-2,4-hexanedionato]bis(2-phenylpyridine)iridium(III) (hereinafter abbreviated as Ir(PPy)₂[1-(OH-Ph-Me)-acac]).

[0674] That is, to a mixture of 71 mg (0.066 mmol) of [Ir(PPy)₂Cl]₂ and47 mg (0.44 mmol) of sodium carbonate was added a solution of 41 mg(0.20 mmol) of 6-(4-hydroxyphenyl)-2,4-hexanedione in 5 ml of DMF andthe mixture was heated at 65° C. for 1 hour with stirring. To thereaction mixture was added dilute hydrochloric acid and chloroform andthe mixture was well shaken. The separated organic layer was dried overmagnesium sulfate and the solvent was distilled off under reducedpressure. The residue was passed through a silica gel column (eluent:amixed solvent of 1:1 (by volume ratio) hexane/ethyl acetate) and asolution having a pale yellow color that eluted next to a small amountof pale yellow byproduct was recovered and concentrated to dryness underreduced pressure. The obtained solid was dissolved in a small amount ofdichloromethane. Addition of hexane to the solution and cooling it to−20° C. afforded 86 mg (0.12 mmol) of the objectiveIr(PPy)₂[1-(OH-Ph-Me)acac] as pale yellow solid. Yield: 92%.Identification was performed by elementary analysis of C, H and N and¹H-NMR.

[0675]¹H-NMR (CDCl₃, ppm): δ 8.48 (d, J=6.2 Hz, 1H, PPy), 8.23 (d, J=5.9Hz, 1H, PPy), 7.9-7.6 (m, 4H, PPy), 7.53 (t, J=7.3 Hz, 2H, PPy), 7.11(t, J=7.0 Hz, 1H, PPy), 6.99 (t, J=7.0 Hz, 1H, PPy), 6.8-6.4 (m, 8H,PPy+C₆H₄OH), 6.27 (t, J=8.1 Hz, 2H, PPy), 5.18 (s, 1H,diketonate-methine), 5.10 (br, 1H, OH), 2.54 (t, J=7.0 Hz, 2H,methylene), 2.31 (m, 2H, methylene), 1.75 (s, 3H, methyl). ElementaryCalcd: C 57.86, H 4.14, N 3.97. (C₃₄H₂₉IrN₂O₃) analysis Found: C 58.03,H 4.11, N 3.86.

[0676]

[0677] (4) As shown in the Reaction Scheme below, theIr(PPy)₂[1-(OH-Ph-Me)acac] was allowed to react with methacryloylchloride to synthesize Ir(PPy)₂[1-(MA-Ph-Me)acac].

[0678] That is, in a nitrogen atmosphere, 169 mg (0.24 mmol) ofIr(PPy)₂[1-(OH-Ph-Me)acac] was dissolved in 10 ml of dichloromethane and0.30 ml (2.2 mmol) of triethylamine was added to the solution. Additionof 0.060 ml (0.61 mmol) of methacryloyl chloride to the obtainedsolution rapidly produced a product. After further adding a small amountof methanol to the solution, the solvent was distilled off under reducedpressure. The residue was passed through a silica gel column with usinga mixed solvent of hexane/dichloromethane/acetone (10:10:1(by volumeratio)) to separate a main product having a yellow color. Afterdistilling off the solvent under reduced pressure, recrystallization ofthe residue from a mixed solvent of dichloromethane/hexane afforded 141mg (0.18 mmol) of the objective Ir(PPy)₂[1-(MA-Ph-Me)acac] as yellowsolid. Yield: 76%. Identification was performed by elementary analysisof C, H and N and ¹H-NMR.

[0679]¹H-NMR (CDCl₃, ppm): δ 8.48 (d, J=5.1 Hz, 1H, PPy), 8.27 (d, J=5.9Hz, 1H, PPy), 7.9-7.5 (m, 6H, PPy), 7.12 (t, J=7.0 Hz, 1H, PPy), 7.04(t, J=7.0 Hz, 1H, PPy), 6.9-6.6 (m, 8H, aromatic), 6.33 (s, 1H,olefinic), 6.27 (d, J=7.6 Hz, 2H, PPy), 5.74 (s, 1H, olefinic), 5.17 (s,1H, diketonate-methine), 2.61 (t, J=7.0 Hz, 2H, ethylene), 2.34 (m, 2H,ethylene), 2.07 (s, 3H, methacryl-methyl), 1.76.(s, 3H,diketonate-methyl). Elementary Calcd: C 58.98, H 4.30, N 3.62.(C₃₈H₃₃IrN₂O₄) analysis Found: C 58.69, H 4.17, N 3.81.

[0680]

EXAMPLE 42 Synthesis of a Polymerizable Compound(1-methacryloyloxy-2,4-pentanedionato)bis(2-phenylpyridine)iridium (III)(hereinafter abbreviated as Ir(PPy)₂(1-MA-acac))

[0681] (1) As shown in the Reaction Scheme below,di(R-chloro)-tetrakis(2-phenylpyridine)diiridium (III) ([Ir(PPy)₂Cl]₂)synthesized by a conventional method and(1-tert-butyldimethylsilyloxy)-2,4-pentanedione synthesized byreferencing the known method (EP Patent No. 0514217) were allowed toreact to synthesize(1-hydroxy-2,4-pentanedionato)bis(2-phenyl-pyridine)iridium (III)(hereinafter abbreviated as Ir(PPy)₂(1-OH-acac)).

[0682] That is, to a solution of 492 mg (0.46mmol) of [Ir(PPy)₂Cl]₂ and139 mg (1.31 mmol) of sodium carbonate in 10 ml of DMF was added 321 mg(1.39 mmol) of1-(tert-butyldimethylsilyloxy)-2,4-pentandione(1-TBDMSO-2,4-pentadione)and the mixture was heated at 70° C. for 1 hour with stirring. Thereaction mixture was cooled to room temperature and 100 ml of asaturated aqueous solution of ammonium chloride and 50 ml of chloroformwere added thereto, and well shaken. The organic layer was dried overmagnesium sulfate and the solvent was distilled off under reducedpressure. The residue was passed through a silica gel column withdichloromethane as an eluent to obtain a yellow solution. This solutionwas concentrated to dryness under reduced pressure to obtain yellowsolid, which was dissolved in 20 ml of THF and 0.46 ml (0.46 mmol) of a1.0 M THF solution of tetra-n-butylammonium fluoride (hereinafterabbreviated as Bu^(n) ₄NF) was dripped thereto while vigorously stirringthe solution. The reaction mixture was stirred at room temperature for0.5 hour and then the solvent was distilled off under reduced pressure.The residue was passed through a silica gel column (eluent: a mixedsolvent of hexane/dichloromethane/acetone (1:3:1 (by volume ratio)) andthe eluted yellow-colored main product was recovered and dried underreduced pressure. Recrystallization of the obtained crude product from amixed solvent of dichloromethane/hexane afforded 389 mg (0.63 mmol) ofthe objective Ir(PPy)₂(1-OH-acac) as yellow solid. Yield: 69%.Identification was performed by elementary analysis of C, H and N and¹H-NMR.

[0683]¹H-NMR (CDCl₃, ppm): δ 8.48 (d, J=5.7 Hz, 1H, PPy), 8.42 (d, J=5.7Hz, 1H, PPy), 7.86 (m, 2H, PPy), 7.74 (t, J=7.6 Hz, 2H, PPy), 7.54 (t,J=5.9 Hz, 2H, PPy), 7.14 (t, J=5.9 Hz, 2H, PPy), 6.82 (t, J=7.3 Hz, 2H,PPy), 6.69 (m, 2H, PPy), 6.28 (d, J=6.8 Hz, 1H, PPy), 6.23 (d, J=6.5 Hz,1H, PPy), 5.17 (S, 1H, diketonate-methine), 3.88 (dd, J=8.1, 5.4 Hz, 1H,—CHH′—O—), 3.78 (dd, J=8.1, 4.3 Hz, 1H, —CHH′—O—), 3.10 (t, J=4.6 Hz,1H, OH), 1.82 (s, 3H, methyl). Elementary Calcd: C 52.67, H 3.77, N4.55. (C₂₇H₂₃IrN₂O₃) analysis Found: C 52.45, H 3.68, N 4.79.

[0684]

[0685] (2) As shown in the Reaction Scheme below, the obtainedIr(PPy)₂(1-OH-acac) and methacryloyl chloride were allowed to react tosynthesize Ir(PPy)₂(1-MA-acac).

[0686] That is, to a solution of 200 mg (0.32 mmol) ofIr(PPy)₂(1-OH-acac) in 15 ml of dichloromethane were added 0.25 ml (1.8mmol) of triethylamine and 0.20 ml (2.0 mmol) of methacryloyl chlorideand the mixture was stirred at room temperature for 1 hour. Then, thereaction mixture was washed with 20 ml of an aqueous solution of sodiumcarbonate and the solvent was distilled off under reduced pressure. Theresidue was dissolved again in dichloromethane and the solution wascharged to the upper part of a silica gel column and developed with amixed solvent of hexane/dichloromethane/acetone of 2:4:1 (by volumeratio). The yellow solution initially obtained was recovered and driedunder reduced pressure to obtain 165 mg (0.24 mmol) of the objectiveIr(PPy)₂(1-MA-acac) as yellow solid. Yield: 74%. Identification wasperformed by elementary analysis of C, H and N and ¹H-NMR.

[0687]¹H-NMR (CDCl₃, ppm): δ 8.53 (d, J=5.7 Hz, 1H, PPy), 8.48 (d, J=5.4Hz, 1H, PPy), 7.84 (d, J=7.8 Hz, 2H, PPy), 7.73 (t, J=7.0 Hz, 2H, PPy),7.53 (t, J=6.8 Hz, 2H, PPy), 5.14 (m, 2H, PPy), 6.79 (m, 2H, PPy), 6.69(m, 2H, PPy), 6.29 (d, J=7.6 Hz, 1H, PPy), 6.23 (d, J=7.6 Hz, 1H, PPy),6.04 (s, 1H, olefinic), 5.51 (s, 1H, olefinic), 5.31 (s, 1H,diketonate-methine), 4.38 (d, J=15.4 Hz, 1H, —CHH′—OC(═O)—), 4.27 (d,J=14.9 Hz, 1H, —CHH′—OC(═O)—), 1.87 (s, 3H, methacryl-methyl), 1.82 (s,3H, diketonate-methyl). Elementary Calcd: C 54.45, H 3.98, N 4.10.(C₃₁H₂₇IrN₂O₄) analysis Found: C 54.18, H 3.96, N 4.33.

[0688]

EXAMPLE 43 Synthesis of a Polymerizable Compound[6-(4-vinylphenyl)-2,4-hexanedionato]bis[2-(2,4-difluorophenyl)pyridine)iridium(III) (hereinafter abbreviated as Ir(2,4-F—PPy)₂[1-(St-Me)-acac])

[0689] (1) As shown in the Reaction Scheme below,2-(2,4-difluorophenyl)pyridine was synthesized by a conventional method.

[0690] That is, under argon stream, 8.69 g (55.0 mmol) of2-bromopyridine was dissolved in 200 ml of dry tetrahydrofuran andcooled to −78° C. To this was dripped 38.7 ml (61.9 mmol) of a 1.6 Mhexane solution of n-butyllithium over 30 minutes. After completion ofthe dripping, further a solution of 7.5 g (55.0 mmol) of zinc chloridein 50 ml of dry tetrahydrofuran was dripped over 30 minutes. Aftercompletion of the dripping, the temperature of the mixture was slowlyelevated to 0° C. and 9.65 g (55.0 mmol) of 1-bromo-2,4-difluorobenzeneand 2.31 g (2.0 mmol) of tetrakis(triphenylphosphine)palladium (0) wereadded thereto. The mixture was stirred for 6 hours under reflux and then200 ml of saturated saline was added to the reaction mixture, followedby extraction of the reaction mixture with diethyl ether. After dryingthe extract, concentration and purification by column chromatography(silica gel; chloroform/hexane (1/1: volume ratio)) afforded 6.00 g(31.4 mmol) of 2-(2,4-difluorophenyl)pyridine as colorless transparentoil. Yield: 63%. Identification was performed by elementary analysis of¹H-NMR and elementary analysis of C, H and N.

[0691]¹H-NMR (CDCl₃, ppm): δ 8.71(d, 1H, J=4.6 Hz), 8.00(td, 1H, J=8.9,6.5 Hz), 7.8-7.7(m, 2H), 7.3-7.2(overlapped with CHCl₃, 1H), 7.1-6.8(m,2H). Elementary analysis Calcd: C 69.11, H 3.69, N 7.33. Found: C 68.98,H 3.80, N 7.31.

[0692]

[0693] (2) As shown in the Reaction Scheme below, the obtained2-(2,4-difluorophenyl)pyridine was allowed to react with sodiumhexachloroiridate n-hydrate by a conventional method to synthesizedi(μ-chloro)tetrakis[2-(2,4-difluorophenyl)-pyridine)diiridium (III)(hereinafter abbreviated as [Ir(2,4-F—PPy)₂Cl]₂).

[0694] That is, 0.96 g (5.0 mmol) of 2-(2,4-difluorophenyl)pyridine and1.00 g of sodium hexachloroiridate n-hydrate were dissolved in 40 ml ofa 3:1 mixed solvent of 2-ethoxyethanol and water (by volume ratio) andargon gas was blown therein for 30 minutes and the mixture was stirredfor 5 hours under reflux. The formed precipitate was collected byfiltration and washed with ethanol and then with a small amount ofacetone, followed by drying in vacuum for 5 hours to obtain 0.79 g (0.65mmol) of the objective [Ir(2,4-F—PPy)₂Cl]₂ as yellow powder. Yield: 86%.Identification was performed by ¹H-NMR and elementary analysis of C, Hand N.

[0695]¹H-NMR (CDCl₃, ppm): δ 9.12(d, 4H, J=5.7 Hz), 8.31(d, 4H, J=8.6Hz), 7.83(dd, 4H, J=7.6, 7.6 Hz), 6.82(dd, 4H, J=7.3, 7.3 Hz), 6.34(ddd,4H, J=11.6, 10.0, 2.4 Hz), 5.29(dd, 4H, J=9.5, 2.4 Hz). Elementaryanalysis Calcd: C 43.46, H 1.99, N 4.61. Found: C 43.39, H 2.03, N 4.55.

[0696]

[0697] (3) As shown in the Reaction Scheme below, [Ir(2,4-F—PPy)₂Cl]₂and 6-(4-vinylphenyl)-2,4-hexanedione were allowed to react tosynthesize Ir(2,4-F—PPy)[1-(St-Me)-acac].

[0698] That is, 243 mg (0.20 mmol) of [Ir(2,4-F—PPy)₂Cl]₂, 212 mg (2.00mmol) of sodium carbonate, and 1.3 mg of2,6-di-tert-butyl-4-methylphenol, and 130 mg (0.60 mmol) of⁶-(4-vinyl-phenyl)-2,4-hexanedione synthesized in the same manner as inExample 38 were dissolved in 20 ml of DMF under argon stream and stirredat 80° C. for 2 hours and then water was added to the reaction mixture,followed by extraction with chloroform. After drying the extract,concentration and purification by column chromatography (silica gel;chloroform), followed by recrystallization from a chloroform/hexanesolution afforded 261 mg (0.33mmol) of Ir(2,4-F—PPy)[1-(St-Me)-acac] asyellow crystal. Yield: 83%. Identification was performed by elementaryanalysis of C, H and N and ¹H-NMR.

[0699]¹H-NMR (CDCl₃, ppm): δ 8.39(d, 1H, J=5.7 Hz), 8.3-8.2(m, 2H),8.04(d, 1H, J=5.7 Hz), 7.8-7.7(m, 2H), 7.19(d, 2H, J=7.8 Hz), 7.15(dd,1H, J=6.6, 6.6 Hz), 6.97(dd, 1H, J=6.6, 6.6 Hz), 6.89(d, 2H, J=7.8 Hz),6.67(dd, 1H, J=17.6, 10.8 Hz), 0.6.4-6.2(m, 2H), 5.7-5.6(m, 3 H),5.22(s, 1H), 5.21(d, 1H, J=11.1 Hz), 2.62(t, 2H, J=7.0 Hz), 2.39(m, 2H),1.78(s, 3 H). Elementary analysis Calcd: C 54.88, H 3.45, N 3.56. Found:C 54.82, H 3.50, N 3.49.

[0700]

EXAMPLE 44 Synthesis of a Polymerizable Compound{3-[4-(2-methacryloyloxyethyl)carbamoyloxyphenylmethyl]-2,4-pentane-dionato}bis(2-phenylpyridine)iridium(III) (hereinafter abbreviated as Ir(PPy)₂[3-(MOI-Ph-Me)acac])

[0701] (1) As shown in the Reaction Scheme below,di(>-chloro)-tetrakis(2-phenylpyridine)diiridium (III) ([Ir(PPy)₂Cl]₂)and 3-(4-hydroxyphenylmethyl)-2,4-pentanedione synthesized byconventional methods were allowed to react to synthesize[3-(4-hydroxyphenylmethyl)-2,4-pentanedionato]bis(2-phenyl-pyridine)iridium(III) (hereinafter abbreviated as Ir(PPy)₂[3-(OH-Ph-Me)-acac]).

[0702] That is, 56 mg (0.052 mmol) of [Ir(PPy)₂Cl]₂ and 44 mg (0.42mmol) of sodium carbonate were dissolved in 5 ml of DMF. To thissolution was added a solution of 30 mg (0.15 mmol) of3-(4-hydroxyphenylmethyl)-2,4-pentanedione synthesized by the knownmethod (C. Cativiela, et al., J. Org. Chem., 60, 3074 (1995)) in 5 ml ofDMF and the mixture was heated at 80° C. for 1.5 hours with stirring.Then to the reaction mixture cooled to room temperature were addeddilute hydrochloric acid and chloroform and the mixture was well shaken.The organic layer was separated and the solvent was distilled off byusing a rotary evaporator and the residue was passed through a silicagel column with a mixed solvent of hexane/ethyl acetate of 1:1 (byvolume ratio) as an eluent to separate a band of a main product.Distilling off the solvent from the obtained pale yellow solution andrecrystallization of the residue from a mixed solution ofdichloromethane/hexane afforded 34mg (0.048 mmol) ofIr(PPy)₂(3-(OH-Ph-Me)-acac] as pale yellow solid. Yield: 46%.Identification was performed by elementary analysis of C, H and N and¹H-NMR.

[0703]¹H-NMR (CDCl₃, ppm): δ 8.58 (d, J=5.9 Hz, 2H, PPy), 7.84 (d, J=7.8Hz, 2H, PPy), 7.73 (t, J=6.5 Hz, 2H, PPy), 7.55 (d, J=7.6 Hz, 2H, PPy),7.1-6.6 (m, 10H, aromatic), 6.27 (d, J=7.6 Hz, 2H, PPy), 4.86 (br-s, 1H,OH), 3.62 (s, 2H, benzyl), 1.80 (s, 6H, methyl). Elementary Calcd: C57.86, H 4.14, N 3.97. (C₃₄H₂₉IrN₂O₃) analysis Found: C 57.97, H 4.22, N4.15.

[0704]

[0705] (2) As shown in the Reaction Scheme below, the obtainedIr(PPy)₂[3-(OH-Ph-Me)-acac] and 2-methacryloyloxyethyl isocyanate (Tradename “Karenz MOI”, manufactured by Showa Denko K. K., hereinaftersometimes referred to as “MOI”) were allowed to react to synthesizeIr(PPy)₂[3-(MOI-Ph-Me)-acac].

[0706] That is, a solution of 71 mg (0.10 mmol) ofIr(PPy)₂[3-(OH—Ph-Me)-acac], 3 mg (0.014 mmol) of2,6-di-tert-butyl-4-methylphenol, 27 mg (0.12 mmol) of dibutyltin (IV)dilaurate and 10 55 mg (0.35 mmol) of MOI in 10 ml of THF was heated at70° C. for 2 hours with stirring. The obtained reaction mixture wasconcentrated to dryness under reduced pressure by using a rotaryevaporator and the residue was passed through a silica gel column with amixed solvent of hexane/ethyl acetate of 1:1 (by volume ratio) as aneluent. The pale yellow solution eluted next to the initially elutedpale yellow byproduct was recovered and concentrated to dryness underreduced pressure. The obtained solid was dissolved in a small amount ofdichloromethane and hexane was added thereto to form precipitate, whichwas collected by filtration and dried under reduced pressure to obtain59 mg (0.069 mmol) of the objective Ir(PPy)₂[3-(MOI-Ph-Me)-acac] as paleyellow solid. Yield: 68%. Identification was performed by elementaryanalysis of C, H and N and ¹H-NMR.

[0707]¹H-NMR (CDCl₃, ppm): δ 8.58 (d, J=5.9 Hz, 2H, PPy), 7.88 (d, J=7.8Hz, 2H, PPy), 7.76 (t, J=6.5 Hz, 2H, PPy), 7.57 (d, J=7. 6 Hz, 2H, PPy),7.2-6.6 (m, 10H, aromatic), 6.27 (d, J=7.6 Hz, 2H, PPy), 6.16 (s, 1H,olefinic), 5.63 (s, 1H, olefinic), 5.31 (br-s, 1H, NH), 4.31 (m, 2H,ethylene), 3.69 (s, 2H, benzyl), 3.59 (m, 2H, ethylene), 1.98 (s, 3H,methacryl-methyl), 1.80 (s, 6H, diketonate-methyl). Elementary Calcd: C57.20, H 4.45, N 4.88. (C₄₁H₃₈IrN₃O₆) analysis Found: C 57.36, H 4.43, N4.91.

[0708]

EXAMPLE 45 Synthesis of a Polymerizable Compoundbis(2-(2,4-difluorophenyl)pyridinato)(3-methacryloyloxypicolinato)Iridium(III) (hereinafter abbreviated as Ir(2,4-F—PPy)₂(3-MA-pic)).

[0709] (1) As shown in the Reaction Scheme below,bis(2-(2,4-difluorophenyl)pyridinato)(3-hydroxypicolinato)Iridium (III)(hereinafter abbreviated as Ir(2,4-F—PPy)₂(3-OH-pic)) was synthesized.

[0710] That is, 10 ml of dry N,N-dimethylformamide (DMF) was added to121.6 mg (0.1 mmol) of [Ir(2,4-F—PPy)₂Cl]₂) prepared in the same manneras in Example 43(1) and (2), 41.7 mg (0.3 mmol) of 3-hydroxypicolinicacid, and 106.0 mg (1.0 mmol) of sodium carbonate under argon stream andthe mixture was stirred at 80° C. for 2 hours. After adding 50 ml ofwater, the reaction mixture was extracted with ethyl acetate. Afterdrying the obtained solution over magnesium sulfate, it was concentratedand purified by column chromatography (silica gel,methanol:chloroform=3:97 (by volume ratio)). Recrystallization fromhexane/chloroform afforded 101.0 mg of Ir(2,4-F—PPy)₂(3-OH-pic) asyellow crystal. Yield: 71%. Identification was performed by elementaryanalysis of C, H and N and ¹H-NMR.

[0711]¹H-NMR (DMSO-d₆, ppm): δ 13.6(br, 1H), 8.50(d, 1H, J=5.9 Hz),8.25(d, 2H, J=11.1 Hz), 8.1-8.0(m, 2H), 7.69(d, 1H, J=5.7 Hz), 7.62(d,1H, J=8.1 Hz), 7.53(d, 1H, J=4.6 Hz), 7.50(d, 1H, J=5.7 Hz), 7.36(t, 1H,J=4.5Hz), 7.24(d, 1H, J=5.1 Hz), 6.9-6.7(m, 2H), 5.66(dd, 1H, J=8.6, 2.4Hz), 5.48(dd, 1H, J=8.6, 2.4 Hz). Elementary analysis Calcd: C 47.32, H2.27, N 5.91. Found: C 47.29, H 2.33, N 5.86.

[0712]

[0713] (2) As shown in the Reaction Scheme below,Ir(2,4-F-PPY)₂(3-MA-pic) was synthesized.

[0714] That is, 71.1 mg (0.10 mmol) of Ir(2,4-F—PPy)₂(3-OH-pic) and 0.2mg of 2,6-di-t-butyl-4-methylphenol were dissolved in 10 ml of drydichloromethane under argon stream and 101.2 mg (1.0 mmol) oftriethylamine, and 52.3 mg (0.50 mmol) of methacryloyl chloride wereadded to the solution, followed by stirring the mixture at roomtemperature for 2 hours. To the reaction mixture was added 50 ml ofwater and then the reaction mixture was extracted with chloroform. Afterdrying the obtained solution over magnesium sulfate, it was concentratedand purified by column chromatography (silica gel, methanol:chloroform=1:24 (by volume ratio)). Recrystallization of the purifiedproduct from hexane/chloroform afforded 63.1 mg ofIr(2,4-F—PPy)₂(3-MA-pic) as yellow crystal. Yield: 81%. Identificationwas performed by ¹H-NMR and elementary analysis of C, H and N.

[0715]¹H-NMR (DMSO-d₆, ppm): δ 8.51(d, 1H, J=5.4 Hz), 8.3-8.2(m, 2H),8.1-7.9(m, 3 H), 7.8-7.6(m, 3 H), 7.52(dd, 1H, J=6.6, 6.6 Hz), 7.35(dd,1H, J=6.6, 6.6 Hz), 6.9-6.7(m, 2H), 6.26(s, 1H), 5.88(s 1H), 5.68(dd,1H, J=8.4, 2.4 Hz), 5.44(dd, 1H, J=8.4, 2.4 Hz), 2.00(s, 3 H).Elementary analysis Calcd: C 49.36, H 2.59, N 5.40. Found: C 49.33, H2.60, N 5.41.

[0716]

EXAMPLE 46 Synthesis of a Polymerizable Compoundbis(2-(2,4-difluorophenyl)pyridinato)(5-methacryloyloxymethyl-picolinato)Iridium(III) (hereinafter abbreviated as Ir(2,4-F—PPy)₂(5-CH₂MA-pic)).

[0717] (1) As shown in the Reaction Scheme below,bis(2-(2,4-difluorophenyl)pyridinato)(5-(hydroxymethyl)picolinato)Iridium(III) (hereinafter abbreviated as Ir(2,4-F—PPy)₂(5-CH₂OH-pic)) wassynthesized.

[0718] That is, 10 ml of dry N,N-dimethylformamide (DMF) was added to121.6 mg (0.1 mmol) of [Ir(2,4-F—PPy)₂Cl]₂), 45.9 mg (0.3 mmol) of5-hydroxymethylpicolinic acid, and 106.0 mg (1.0 mmol) of sodiumcarbonate under argon stream and the mixture was stirred at 80° C. for 2hours. After adding 50 ml of water, the reaction mixture was extractedwith ethyl acetate. After drying the obtained solution over magnesiumsulfate, it was concentrated and purified by column chromatography(silica gel, methanol:chloroform=1:19 (by volume ratio)).Recrystallization from hexane/chloroform afforded 108.7 mg ofIr(2,4-F—PPy)₂(5-CH₂OH-pic) as yellow crystal. Yield: 75%.Identification was performed by ¹H-NMR and elementary analysis of C, Hand N.

[0719]¹H-NMR (DMSO-d₆, ppm): δ 8.54(d, 1H, J=4.6 Hz), 8.3-8.2(m, 2H),8.1-8.0(m, 4 H), 7.70(s, 1H), 7.61(d, 1H, J=4.9 Hz), 7.49(dd, 1H, J=6.6Hz, 6.6 Hz), 7.32(dd, 1H, J=6.6 Hz, 6.6 Hz), 6.9-6.7(m, 2H), 5.71(dd,1H, J=8.9 Hz, 2.4 Hz), 5.46(dd, 1H, J=8.5 Hz, 2.3 Hz), 5.42(t, 1H, J=4.6Hz), 4.49(d, 2H, J=4.6 Hz). Elementary analysis Calcd: C 48.06, H 2.50,N 5.80. Found: C 48.05, H 2.54, N 5.86.

[0720]

[0721] (2) As shown in the Reaction Scheme below,Ir(2,4-F—PPy)₂(5-CH₂MA-pic) was synthesized.

[0722] That is, 72.5 mg (0.1 mmol) of Ir(2,4-F—PPy)₂(5-CH₂OH-pic) and0.2 mg of 2,6-di-t-butyl-4-methylphenol were dissolved in 10 ml of drydichloromethane under argon stream and 101.2 mg (1.0 mmol) oftriethylamine, and 52.3 mg (0.5 mmol) of methacryloyl chloride wereadded to the solution, followed by stirring,the mixture at roomtemperature for 2 hours. To the reaction mixture was added 50 ml ofwater and then the reaction mixture was extracted with chloroform. Afterdrying the obtained solution over magnesium sulfate, it was concentratedand purified by column chromatography (silica gel, methanol:chloroform=3:97 (by volume ratio)). Recrystallization of the purifiedproduct from hexane/chloroform afforded 70.6 mg ofIr(2,4-F—PPy)₂(5-CH₂MA-pic) as yellow crystal. Yield: 89%.Identification was performed by ¹H-NMR and elementary analysis of C, Hand N.

[0723]¹H-NMR (DMSO-d₆, ppm): δ 8.53(d, 1H, J=5.1 Hz), 8.28(d, 1H, J=8.4Hz), 8.22(d, 1H, J=8.6 Hz), 8.1-8.0(m, 4 H), 7.70(s, 1H), 7.66(d, 1H,J=4.9 Hz), 7.48(dd, 1H, J=6.5 Hz, 6.5 Hz), 7.31(dd, 1H, J=6.5 Hz, 6.5Hz), 6.9-6.7(m, 2H), 5.84(s, 1H), 5.7-5.6(m, 2H), 5.47(dd, 1H, J=8.8 Hz,2.6 Hz), 5.24(d, 2H, J=2.7 Hz), 1.78(s, 3 H). Elementary analysis Calcd:C 50.00, H 2.80, N 5.30. Found: C 49.92, H 2.87, N 5.28.

[0724]

EXAMPLE 47 Synthesis of a Polymerizable Compoundbis(2-(2,4-difluorophenyl)pyridinato)(5-(2-(methacryloyloxy)ethyl-carbamoyloxymethyl)picolinato)Iridium(III) (hereinafter abbreviated as Ir(2,4-F—PPy)₂(5-CH₂MOI-pic)).

[0725] As shown in the Reaction Scheme below,Ir(2,4-F—PPy)₂(5-CH₂MOI-pic) was synthesized.

[0726] That is, 72.5 mg (0.1 mmol) of Ir(2,4-F—PPy)₂(5-CH₂OH-pic) as theintermediate in Example 46, 0.2 mg of 2,6-di-t-butyl-4-methylphenol(BHT) and 1.3 mg of dibutyltin (IV) dilaurate (DBTL) were dissolved in10 ml of dry tetrahydrofuran. To this was added 31.0 mg (0.2 mmol) of2-methacryloyloxyethyl isocyanate (Trade name “Karenz MOI”, manufacturedby Showa Denko K. K., hereinafter sometimes referred to as “MOI”) andthe mixture was stirred at 50° C. for 1 hour. To the reaction mixturewas added 50 ml of water and then the reaction mixture was extractedwith chloroform. After drying the obtained solution over magnesiumsulfate, it was concentrated and purified by column chromatography(silica gel, methanol:chloroform=3:97 (by volume ratio)).Recrystallization of the purified product from hexane/chloroformafforded 76.4 mg of Ir(2,4-F—PPy)₂(5-CH₂MOI-pic) as yellow crystal.Yield: 87%. Identification was performed by ¹H-NMR and elementaryanalysis of C, H and N.

[0727]¹H-NMR (DMSO-d₆, ppm): δ 8.53(d, 1H, J=5.1 Hz), 8.32(dd, 2H,J=8.0, 1.8 Hz), 8.25(d, 1H, J=8.9 Hz), 8.22(d, 1H, J=9.2 Hz), 8.1-8.0(m,3 H), 7.60(d, 1H, J=4.6 Hz), 7.51(dd, 1H, J=6.5, 6.5 Hz), 7.35(dd, 1H,J=6.5, 6.5 Hz), 6.9-6.7(m, 2H), 6.10(s, 1H), 5.87(s, 1H), 5.71(dd, 1H,J=8.4, 2.2 Hz), 5.46(dd, 1H, J=8.8, 2.6 Hz), 4.90(s, 2H), 4.23(t, 2H,J=1.9 Hz), 3.47(m, 2H), 1.90(s, 3 H). Elementary analysis Calcd: C50.62, H 3.33, N 6.38. Found: C 50.59, H 3.35, N 6.32.

[0728]

EXAMPLE 48 Synthesis of a Polymerizable Compound bis(2-(2,4-difluorophenyl)pyridinato)(5-(2-(methacryloyloxy)-ethoxycarbonyl)picolinato)Iridium(III) (hereinafter abbreviated as Ir(2,4-F—PPy)₂(5-COHEMA-pic)).

[0729] (1) As shown in the Reaction Scheme below,bis(2-(2,4-difluorophenyl)pyridinato)(5-carboxypicolinato)Iridium (III)(hereinafter abbreviated as Ir(2,4-F—PPy)₂(5-COOH-pic))was synthesized.

[0730] That is, 10 ml of dry N,N-dimethylformamide was added to 243.2 mg(0.2 mmol) of Ir[(2,4-F—PPy)₂Cl]₂, 100.3 mg (0.6 mmol) of2,5-pyridinedicarboxylic acid, and 212.0 mg (2.0 mmol) of sodiumcarbonate and the mixture was stirred at 80° C. for 2 hours. To thereaction mixture was added 50 ml of 1 N hydrochloric acid to precipitatethe product, which was filtered. This was dissolved in a small amount ofchloroform and purified using column chromatography (silica gel,methanol:chloroform=1:4). Further, reprecipitation of the purifiedproduct from hexane/ethanol afforded 204.0 mg ofIr(2,4-F—PPy)₂(5-COOH-pic) as yellow crystal. Yield: 69%. Identificationwas performed by ¹H-NMR and elementary analysis of C, H and N.

[0731]¹H-NMR (DMSO-d₆, ppm): δ 10.7(s, 1H), 8.53(d, 1H, J=5.1 Hz),8.37(dd, 2H, J=8.0, 1.8 Hz), 8.28(d, 1H, J=8.9 Hz), 8.25(d, 1H, J=9.2Hz), 8.1-8.0(m, 3H), 7.59(d, 1H, J=4.6 Hz), 7.47(dd, 1H, J=6.5, 6.5 Hz),7.32(dd, 1H, J=6.5, 6.5 Hz), 6.9-6.7(m, 2H), 5.70(dd, 1H, J=8.4, 2.2Hz), 5.48(dd, 1H, J=8.8, 2.6 Hz). Elementary analysis Calcd: C 47.15, H2.18, N 5.69. Found: C 47.10, H 2.28, N 5.66.

[0732]

[0733] (2) As shown in the Reaction Scheme below,Ir(2,4-F—PPY)₂(5-COHEMA-pic) was synthesized.

[0734] That is, 73.9 mg (0. 1 mmol) of Ir(2,4-F—PPy)₂(5-COOH-pic), 52.5mg (0.2 mmol) of triphenylphoshine (PPh₃), 19.5 mg (0.15 mmol) of2-hydroxyethyl methacrylate were dissolved in 10 ml of dry THF underargon streamand 65.3mg (0.15mmol) of a 40% toluene solution of diethylazodicarboxylate (DEAD) was dripped thereto at −20° C. The mixture wasleft to stand as it was while the temperature was elevated to roomtemperature and the mixture was stirred for 2 hours. After completion ofthe reaction, the solvent was distilled off and the reaction mixture wasconcentrated to dryness. Then the residue was dissolved in a smallamount of chloroform and purified using column chromatography (silicagel, methanol:chloroform=1:19 (by volume ratio)). Recrystallization ofthe purified product from hexane/chloroform afforded 61.5 mg ofIr(2,4-F—PPy)₂(5-COHEMA-pic) as-yellow crystal. Yield: 72%.Identification was performed by ¹H-NMR and elementary analysis of C, Hand N.

[0735]¹H-NMR (DMSO-d₆, ppm): δ 8.54(d, 1H, J=5.1 Hz), 8.37(dd, 2H,J=8.0, 1.8 Hz), 8.31(d, 1H, J=8.9 Hz), 8.27(d, 1H, J=9.2 Hz), 8.1-8.0(m,3 H), 7.57(d, 1H, J=4.6 Hz), 7.46(dd, 1H, J=6.5, 6.5 Hz), 7.32(dd, 1H,J=6.5, 6.5 Hz), 6.9-6.7(m, 2H), 6.10(s, 1H), 5.87(s, 1H), 5.71(dd, 1H,J=8.4, 2.2 Hz), 5.51(dd, 1H, J=8.8, 2.6 Hz), 4.64(t, 2H, J=2.0 Hz),4.55(t, 2H, J=2.0 Hz), 1.93(s, 3 H). Elementary analysis Calcd: C 49.41,H 2.84, N 4.94. Found: C 49.38, H 2.88, N 4.95.

[0736]

EXAMPLE 49 Synthesis of a Polymerizable Compoundbis(2-(2,4-difluorophenyl)pyridinato)(3-(4-(vinylphenyl)methoxy-picolinato)Iridium(III) (hereinafter abbreviated as Ir(2,4-F—PPy)₂(3-ST-pic)).

[0737] As shown in the Reaction Scheme below, Ir(2,4-F—PPy)₂(3-ST-pic)was synthesized.

[0738] That is, 5 ml of dry N,N-dimethylformamide was added to 35.5 mg(0.05 mmol) of Ir(2,4-F—PPy)₂(3-OH-pic) as the intermediate in Example45, 69.1 mg (0.5 mmol) of potassium carbonate, and 0.1 mg of2,6-di-t-butyl-4-methylphenol under argon stream and 30.5 mg (0.2 mmol)of 4-vinylbenzyl chloride was further added thereto. The mixture wasstirred at 80° C. for 4 hours. To the reaction mixture was added 50 mlof water to precipitate the product, which was collected by filtrationand purified by column chromatography (silica gel,methanol:chloroform=3:97 (by volume ratio)). Recrystallization of thepurified product from hexane/chloroform afforded 24.0 mg ofIr(2,4-F—PPy)₂(3-ST-pic) as yellow crystal. Yield: 58%. Identificationwas performed by ¹H-NMR and elementary analysis of C, H and N.

[0739]¹H-NMR (DMSO-d₆, ppm): δ 8.59(d, 1H, J=5.1 Hz), 8.3-8.2(m, 2H),8.1-8.0(m, 2H), 7.9(d, 1H, J=8.6 Hz), 7.67(d, 1H, J=5.1 Hz), 7.6-7.3(m,7 H), 6.9-6.7(m, 3 H), 5.85(d, 1H, J=17.8 Hz), 5.67(dd, 1H, J=8.9, 2.4Hz), 5.45(dd, 1H, J=8.9, 2.4 Hz), 5.29(s, 2H), 5.27(d, 1H, J=11.1 Hz)Elementary analysis Calcd: C 53.75, H 2.93, N 5.08. Found: C 53.71, H2.90, N 5.03.

[0740]

EXAMPLE 50 Synthesis of a Polymerizable Compoundbis(2-phenylpyridinato)(3-methacryloyloxypicolinato)Iridium (III)(hereinafter abbreviated as Ir(PPy)₂(3-MA-pic))

[0741] (1) As shown in the Reaction Scheme below,bis(2-phenylpyridinato)(3-hydroxypicolinato)Iridium (III) (hereinafterabbreviated as Ir(PPy)₂(3-OH-pic)) was synthesized.

[0742] That is, 10 ml of dry N,N-dimethylformamide (DMF) was added to107.2 mg (0.1 mmol) of di(μ-chloro)tetrakis(2-phenylpyridine)diiridium(III) (hereinafter abbreviated as [Ir(PPy)₂Cl]₂) synthesized by aconventional method, 41.7 mg (0.3 mmol) of 3-hydroxypicolinic acid, and106.0 mg (1.0 mmol) of sodium carbonate under argon stream and themixture was stirred at 80° C. for 2 hours. After adding 50 ml of water,the reaction mixture was extracted with chloroform. After drying theobtained solution over magnesium sulfate, it was concentrated andpurified by column chromatography (silica gel, methanol:chloroform=1:19(by volume ratio)). Recrystallization from hexane/chloroform afforded106.0 mg of Ir(PPy)₂(3-OH-pic) as yellow crystal. Yield: 83%.Identification was performed by ¹H-NMR and elementary analysis of C, Hand N.

[0743]¹H-NMR (DMSO-d₆, ppm): δ 8.46(d, 1H, J=4.9 Hz), 8.23(d, 1H, J=8.1Hz), 8.20(d, 1H, J=8.6 Hz), 8.0-7.9(m, 2H), 7.80(m, 2H), 7.60(dd, 1H,J=5.9, 5.9 Hz), 7.55(d, 1H, J=1.4 Hz), 7.47(dd, 1H, J=8.5, 5.0 Hz),7.40(dd, 1H, J=5.9, 5.9 Hz), 7.26(dd, 1H, J=5.9, 5.9 Hz), 7.16(dd, 1H,J=4.9, 1.4 Hz), 6.90(dd, 1H, J=7.6, 7.6 Hz), 6.87(dd, 1H, J=7.6, 7.6Hz), 6.8-6.7(m, 2H), 6.20(d, 1H, J=7.6 Hz), 6.05(d, 1H, J=7.6 Hz).Elementary analysis Calcd: C 52.65, H 3.16, N 6.58. Found: C 52.62, H3.21, N 6.57.

[0744]

[0745] (2) As shown in the Reaction Scheme below, Ir(PPy)₂(3-MA-pic) wassynthesized.

[0746] That is, 31.9 mg (0.05 mmol) of Ir(PPy)₂(3-OH-pic) and 0.1 mg of2,6-di-t-butyl-4-methylphenol were dissolved in 5 ml of drydichloromethane under argon stream and 50.6 mg (0.5 mmol) oftriethylamine, and 26.1 mg (0.25 mmol) of methacryloyl chloride wereadded to the solution, followed by stirring the mixture at roomtemperature for 2 hours. To the reaction mixture was added 50 ml ofwater and then the reaction mixture was extracted with chloroform. Afterdrying the obtained solution over magnesium sulfate, it was concentratedand purified by column chromatography (silica gel,methanol:chloroform=1:19 (by volume ratio)). Recrystallization of thepurified product from hexane/chloroform afforded 23.0 mg ofIr(PPy)₂(3-MA-pic) as yellow crystal. Yield: 65%. Identification wasperformed by ¹H-NMR and elementary analysis of C, H and N.

[0747]¹H-NMR (DMSO-d₆, ppm): δ 8.50(d, 1H, J=5.7 Hz), 8.23(d, 1H, J=4.9Hz), 8.21(d, 1H, J=5.7 Hz), 8.0-7.9(m, 3 H), 7.81(t, 2H, J=8.9 Hz),7.7-7.5(m, 3 H), 7.42(dd, 1H, J=6.6, 6.6 Hz), 7.25(dd, 1H, J=6.3, 6.3Hz), 6.91(dd, 1H, J=7.6, 7.6 Hz), 6.86(dd, 1H, J=7.6, 7.6 Hz), 6.25(s,1H), 6.22(d, 1H, J=7.8 Hz), 6.01(d, 1H, J=7.3 Hz), 5.87(s, 1H), 2.01(s,3 H). Elementary analysis Calcd: C 54.38, H 3.42, N 5.95. Found: C54.29, H 3.51, N 5.94.

[0748]

EXAMPLE 51 Synthesis ofN-vinylcarbazole/Ir(2,4-F—PPy)₂(3-MA-pic)copolymer (hereinafter,abbreviated as VCz-co-Ir(2,4-F—PPy)₂(3-MA-pic))

[0749] The titled copolymer was synthesized as a light emitting materialcontaining Ir(2, 4-f-PPy)₂(3-MA-pic) as a unit having the function ofluminescence and N-vinylcarbazole as a unit having the function of holetransportation.

[0750] 966 mg (5.0 mmol) of N-vinylcarbazole, 38.9 mg (0.05 mmol) ofIr(2,4-f-PPy)₂(3-MA-pic), and 8.2 mg (0.05 mmol) of AIBN were dissolvedin 25 ml of dry toluene and argon was blown into the obtained solutionfor 1 hour. This solution was warmed up to 80° C. to initiatepolymerization reaction and the reaction mixture was stirred as it wasfor 8 hours. After cooling, the reaction mixture was dripped into 250 mlof methanol to precipitate a polymer, which was recovered by filtration.Further, the recovered polymer was dissolved in 25 mol of chloroform.This solution was purified by dripping it into 250 ml of methanol toreprecipitate the polymer and dried in vacuum at 60° C. for 12 hours toobtain 673 mg of the objective compound VCz-co-Ir(2,4-F—PPy)₂(3-MA-pic).Table 5 shows yields, results of GPC measurements, and Ir complexcontents measured by ICP elementary analyses.

EXAMPLES 52 to 56

[0751] Copolymers were synthesized in the same manner as in Example $1except that the polymerizable compounds prepared in Examples 46 to 50,respectively, were used in place of Ir(2,4-F—PPY)₂(3-MA-pic) Table 5shows yields, results of GPC measurements, and Ir complex contentsmeasured by ICP elementary analyses. TABLE 5 Ir Complex Recovery GPCMeasurement Content Example Polymer (%) Mn Mw Mw/Mn (mol %) 51VCz-co-Ir(2,4- 67 4500 12800 2.84 1.07 F—PPy)₂(3-MA-pic) 52VCz-co-Ir(2,4- 79 4300 13600 3.16 1.04 F—PPy)₂(5-CH₂MA-pic) 53VCz-co-Ir(2,4- 63 5100 14800 2.90 1.02 F—PPy)₂(5-CH₂MOI-pic) 54VCz-co-Ir(2,4- 61 4100 13700 3.34 0.98 F—PPy)₂(5-COHEMA-pic) 55VCz-co-Ir(2,4- 72 4600 11400 2.48 1.04 F—PPy)₂(3-ST-pic) 56 VCz-co- 744400 13000 2.95 1.01 Ir(PPy)₂(3-MA-pic)

EXAMPLES 57 to 62 Fabrication and Evaluation of Organic Light EmittingDevices

[0752] Organic light emitting devices were fabricated by usingITO-substrate (manufactured by Nippo Electric Co., Ltd.) which is 25mm×25 mm glass substrates provided on one side thereof with two ITO(indium tin oxide) electrodes serving as anodes, each being 4 mm inwidth formed in the form of stripes.

[0753] First, poly(3,4-ethylenedioxythiophene)/polystyrene-sulfonic acid(manufactured by Bayer AG, trade name “Baytron P”) was coated on the ITO(anode) of the above-mentioned ITO-substrate by a spin coating methodunder the conditions of 3,500 rpm and a coating time of 40 seconds anddried in a vacuum drier at 60° C. for 2 hours to form an anode bufferlayer. The obtained anode buffer layer had a film thickness of about 50nm.

[0754] Then, a coating solution for forming a layer containing a lightemitting material and an electron transporting material was prepared.21.0 mg of the light emitting material shown in Table 6 and 9.0 mg of2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD)(manufactured by Tokyo Kasei Kogyo Co., Ltd.) as an electrontransporting material were dissolved in 2970 mg of chloroform(manufactured by Wako Pure Chemical Industries, Ltd., reagent grade) andthe obtained solution was filtered through a filter having a pore sizeof 0.2 μm to prepare a coating solution.

[0755] Further, the obtained coating solution was coated on the anodebuffer layer by a spin coating method under the conditions of 3,000 rpmand a coating time of 30 seconds and dried at room temperature (25° C.)for 30 minutes to form a layer containing a light emitting material andan electron transporting material. The obtained layer had a filmthickness of about 100 nm.

[0756] Then, the substrate having formed thereon a layer containing alight emitting material and an electron transporting material was placedin a vapor deposition apparatus and silver and magnesium werecodeposited in a weight ratio of 1:10 to form two cathodes in the formof stripes of 3 mm in width so as to cross the direction of length ofthe anodes at right angles. The obtained cathodes had a film thicknessof about 50 nm.

[0757] Finally, in an argon atmosphere, lead wires (wiring) wereattached to the anodes and cathodes to fabricate four organic lightemitting devices of 4 mm (length)×3 mm (width). Voltage was applied tothe above-mentioned organic EL devices by using a programmable directvoltage/current source TR6143 manufactured by Advantest Corporation tocause luminescence and the luminance was measured by using a luminancemeter BM-8 manufactured by Topcon Corporation. As a result, theluminescence starting voltage and initial luminance at 20 V as shown inTable 6 were obtained (average of four devices for each light emittingmaterial). TABLE 6 20 V Luminescence Initial Light Emitting MaterialStarting Luminance Example Polymer Example voltage (V) (cd/m²) 57VCz-co-Ir(2,4- 54 8 790 F—PPy)₂(3-MA-pic) 58 VCz-co-Ir(2,4- 55 8 500F—PPy)₂(5-CH₂MA-pic) 59 VCz-co-Ir(2,4- 56 9 640 F—PPy)₂(5-CH₂MOI-pic) 60VCz-co-Ir(2,4- 57 8 740 F—PPy)₂(5-COHEMA-pic) 61 VCz-co-Ir(2,4- 58 9 800F—PPy)₂(3-ST-pic) 62 VCz-co-Ir(PPy)₂(3- 59 8 910 MA-pic)

EXAMPLE 63 Synthesis of a Polymerizable Compound[6-(4-vinylphenyl)-2,4-hexanedionato]bis[2-(2-pyridyl)benzo-thienyl)iridium(III) (hereinafter abbreviated as Ir(btp)₂[1-(StMe)-acac])

[0758] As shown in the Reaction Scheme below,6-(4-vinylbiphenyl)-2,4-hexanedione prepared in the same manner as inExample 38(1) anddi(μ-chloro)tetrakis(2-(2-pyridyl)-benzothienyl)diiridium (III)(hereinafter abbreviated as [Ir(btp)₂Cl]₂) synthesized by a conventionalmethod (cf., e.g., S. Lamansky, et al., Inorganic Chemistry, 40, 1704(2001)) were allowed to react to synthesize Ir(btp)₂[1-(StMe)-acac)].

[0759] That is, to a suspension of 253 mg (0.20 mmol) of [Ir(btp)₂Cl]₂in 10 ml of N,N-dimethylformamide (hereinafter abbreviated as DMF) wereadded 161 mg (0.74 mmol) of 6-(4-vinylphenyl)-2,4-hexanedione, 64 mg ofsodium carbonate and 1.9 mg (0.0086 mmol) of2,6-di-tert-butyl-4-methylphenol (hereinafter abbreviated as BHT), andthe mixture was heated at 80° C. for 1 hour with stirring. To thereaction mixture were added 100 ml of water and 50 ml of chloroform andthe obtained mixture was well shaken. The organic layer was dried overmagnesium sulfate and then concentrated to dryness under reducedpressure by using a rotary evaporator. Then, the crude product waspurified through a silica gel column with dichloromethane as an eluentto obtain a reddish brown solution. The solution was concentrated underreduced pressure and hexane was added thereto followed byrecrystallization at −20° C. to obtain 153 mg (0.18 mg) of the objectiveIr(btp)₂[1-(StMe)-acac] as reddish brown solid. Yield: 47%.Identification was performed by elementary analysis of C, H and N and¹H-NMR.

[0760]¹H-NMR (CDCl₃, ppm): δ 8.40 (d, J=5.4 Hz, 1H, btp), 7.97 (d, J=5.4Hz, 1H, btp), 7.65 (m, 6H, btp), 7.1-6.7 (m, 10H, aromatic), 6.63 (dd,J=17.8, 11.1 Hz, 1H, vinylic), 6.24 (d, J=8.1 Hz, 1H, btp), 6.16 (d,J=7.8 Hz, 1H, btp), 5.65 (d, J=17.8 Hz, 1H, vinylic), 5.22 (s, 1H,diketonate-methine), 5.18 (d, J=11.1 Hz, 1H, vinylic), 2.56 (m, 2H,ethylene), 2.37 (m, 2H, ethylene), 1.75 (s, 3H, methyl). Elementaryanalysis Calcd: C 58.02, H 3.77, N 3.38. (C₄₀H₃₁IrN₂O₂S₂) Found: C57.79, H 3.81, N 3.55.

[0761]

EXAMPLE 64 Synthesis of a Polymerizable Compound[6-(4-methacryloyloxyphenyl)-2,4-hexanedionato]bis[2-(2-pyridyl)-benzothienyl]iridium(III) (hereinafter abbreviated as Ir(btp)₂[1-(MA-Ph-Me)-acac])

[0762] (1) As shown in the Reaction Scheme below,6-(4-hydroxyphenyl)-2,4-hexanedione prepared in the same manner as inExample 41(1) and (2) and [Ir(btp)₂Cl]₂ synthesized by a conventionalmethod were allowed to react to synthesize Ir(btp)₂[1-(OH-Ph-Me)-acac)].

[0763] That is, 245 mg (0.19 mmol) of [Ir(btp)2Cl]₂and 111 mg (1.06mmol) of sodium carbonate were dissolved in a solution of 141 mg (0.680mmol) of 6-(4-hydroxyphenyl)-2,4-hexanedione in 10 ml of DMF and themixture was heated at 80° C. for 1.5 hours with stirring. To thereaction mixture cooled to room temperature were added chloroform and anaqueous solution of ammonium chloride, and the obtained mixture was wellshaken. The organic layer was dried over magnesium sulfate and then thesolvent was distilled off by using a rotary evaporator. The residue waspassed through a silica gel column(eluent:hexane/dichlorometahne/acetone=5/10/1 (by volume ratio)) and aband containing a main product having a reddish brown color wasseparated and concentrated to dryness under reduced pressure to obtain215 mg (0.26 mmol) of the objective Ir(btp)₂[1-(OH-Ph-Me)-acac)] asreddish brown solid. Yield: 70%. Identification was performed byelementary analysis of C, H and N and ¹H-NMR.

[0764]¹H-NMR (CDCl₃, ppm): δ 8.40 (d, J=5.4 Hz, 1H, btp), 8.06 (d, J=5.4Hz, 1H, btp), 7.63 (m, 6H, btp), 7.04 (m, 3H, btp), 6.81 (m, 3H, btp),6.66 (d, J=8.4 Hz, 2H, —C₆ H₄—OH), 6.38 (d, J=8.4 Hz, 2H, —C₆H₄—OH),5.22 (s, 1H, diketonate-methine), 5.20 (br, 1H, OH), 2.48 (m, 2H,methylene), 2.31 (m, 2H, methylene), 1.75 (s, 3H, methyl). Elementaryanalysis Calcd: C 55.80, H 3.57, N 3.42. (C₃₈H₂₉IrN₂O₃S₂) Found: C56.19, H 3.57, N 3.31.

[0765]

[0766] (2) As shown in the Reaction Scheme below, the obtainedIr(btp)₂[1-(OH-Ph-Me)-acac] and methacryloyl chloride were allowed toreact to synthesize Ir(btp)₂[1-(MA-Ph-Me)-acac].

[0767] That is, to a solution of 248 mg (0.32 mmol) ofIr(btp)₂[1-(OH-Ph-Me)-acac] in 20 ml of dry dichloromethane were added0.25 ml (1.8 mmol) of triethylamine and 0.20 ml (2.0 mmol) ofmethacryloyl chloride, and the mixture was stirred at room temperaturefor 1 hour. Then, the reaction mixture was washed with 20 ml of anaqueous solution of sodium carbonate and the solvent was distilled offunder reduced pressure. The residue was purified by columnchromatography (eluent:a mixed solvent of hexane/dichloromethane/acetoneof 2:4:1 (by volume ratio)) and the reddish brown solution that wasfirst eluted was separated and dried under reduced pressure to obtain180 mg (0.20 mmol) of the objective Ir(btp)₂[1-(MA-Ph-Me)-acac] asreddish brown solid. Yield: 64%. Identification was performed byelementary analysis of C, H and N and ¹H-NMR. ¹H-NMR (CDCl₃, ppm): δ8.42 (d, J=5.4 Hz, 1H, btp), 8.10 (d, J=5.4 Hz, 1H, btp), 7.65 (m, 6H,btp), 7.1-6.7 (m, 10H, aromatic), 6.40 (d, J=8.1 Hz, 1H, btp), 6.27 (d,J=8.1 Hz, 1H, btp), 6.12 (s, 1H, olefinic), 5.71 (s, 1H, olefinic), 5.19(s, 1H, diketonate-methine), 2.51 (m, 2H, C₂ H₄), 2.39 (m, 2H, C₂ H₄),1.89 (s, 3H, methacryl-methyl), 1.80 (s, 3H, diketonate-methyl).Elementary analysis Calcd: C 56.93, H 3.75, N 3.16. (C₄₂H₃₃IrN₂O₄S₂)Found: C 57.09, H 3.77, N 4.18.

[0768]

EXAMPLE 65 Synthesis of a Polymerizable Compound{6-[4-(2-methacryloyloxy)ethylcarbamoyloxyphenyl]-2,4-hexanedionato}bis[2-(2-pyridyl)benzothienyl)iridium(III) (hereinafter abbreviated as Ir(btp)₂[1-(MOI-Ph-Me)-acac])

[0769] As shown in the Reaction Scheme below,Ir(btp)₂[1-(OH—Ph-Me)-acac] obtained in Example 64 and2-methacryloyloxyethyl isocyanate (Trade name “Karenz MOI”, manufacturedby Showa Denko K. K., hereinafter sometimes referred to as “MOI”) wereallowed to react to synthesize Ir(btp)₂[1-(MOI-Ph-Me)-acac].

[0770] That is, to a solution of 215 mg (0.26 mmol) ofIr(btp)₂[1-(OH-Ph-Me)-acac] in 10 ml of THF were added 4.0 mg (0. 18mmol) of BHT, 35 mg of dibutyltin (IV) dilaurate (hereinafterabbreviated as DBTL) and 401 mg (2.58 mmol) of MOI, and the mixture washeated for 3 hours under reflux in a hot water bath. Then, the reactionmixture cooled to room temperature was dried under reduced pressure andthe residue was purified through a silica gel column (eluent:a mixedsolvent of hexane/dichloro-methane/acetone of 5:10:1 (by volume ratio)).A band containing a main product having a reddish brown color thateluted first was separated and concentrated to dryness under reducedpressure to obtain 223 mg (0.23 mmol) of the objectiveIr(btp)₂[1-(MOI—Ph-Me)-acac)] as reddish brown solid. Yield: 87%.Identification was performed by elementary analysis of C, H and N and¹H-NMR.

[0771]¹H-NMR (CDCl₃, ppm): δ 8.40 (d, J=5.7 Hz, 1H, btp), 8.12 (d, J=5.1Hz, 1H, btp), 7.65 (m, 6H, btp), 7.1-6.7 (m, 10H, aromatic), 6.25 (d,J=8.4 Hz, 1H, btp), 6.20 (d, J=8.1 Hz, 1H, btp), 6.16 (s, 1H, olefinic),5.63 (s, 1H, olefinic), 5.26 (br-s, 1H, NH), 5.21 (s, 1H,diketonate-methine), 4.31 (t, J=5.4 Hz, 2H, N—C₂ H₄—O), 3.59 (t, J=5.4Hz, 2H, N—C₂ H₄—O), 2.55 (m, 2H, C—C₂ H₄—C), 2.34 (m, 2H, C—C₂ H₄—C),1.98 (s, 3H, methacryl-methyl), 1.76 (s, 3H, diketonate-methyl).Elementary analysis Calcd: C 55.54, H 3.94, N 4.32. (C₄₅H₃₈IrN₃O₆S₂)Found: C 55.13, H 3.89, N 4.58.

[0772]

EXAMPLE 66 Synthesis of a Polymerizable Compound[1-(2-methacryloyloxy)ethylcarbamoyloxy-2,4-pentanedionato]bis[2-(2-pyridyl)benzothienyl)iridium(III) (hereinafter abbreviated as Ir(btp)₂(1-MOI-acac)

[0773] (1) As shown in the Reaction Scheme below, [Ir(btp)₂Cl]₂synthesized by a conventional method and(1-tert-butyldimethylsilyloxy)-2,4-pentanedione(1-TBDMSO-2,4-pentanedione) synthesized by referencing the known method(EP Patent No. 0514217) were allowed to react to synthesizeIr(btp)₂(1-OH-acac).

[0774] That is, 449 mg (0.35 mmol) of [Ir(btp)₂Cl]₂and 137 mg (1.29mmol) of sodium carbonate were dissolved in a solution of 310 mg (1.35mmol) of 1-TBDMSO-2, 4-pentanedione in 15 ml of DMF, and the mixture washeated at 80° C. for 1 hour with stirring. The obtained reaction mixturewas cooled to room temperature and chloroform and dilute hydrochloricacid were added thereto, and well shaken. Subsequently, the organiclayer was washed with water, and the solvent was distilled of f underreduced pressure. The residue was purified by silica gel columnchromatography (eluent dichloromethane) and the compound having areddish brown color that eluted first was separated and concentrated todryness under reduced pressure. The obtained solid was dissolved in 10ml of dry THF and 0.60 ml (0.60 mmol) of a 1.0 M THF solution oftetra-n-butylammonium fluoride (n-Bu₄NF) was dripped thereto whilevigorously stirring the mixture. The solution was stirred at roomtemperature for 0.5 hour and then the solvent was distilled off underreduced pressure. The residue was purified by silica gel columnchromatography (eluent:a mixed solvent of hexane/dichloromethane/acetoneof 5:10:2 (by volume ratio)). Separation of a main product having areddish brown color and drying it under reduced pressure afforded 360 mg(0.49 mmol) of the objective Ir(btp) ₂ (I-OH-acac) as reddish brownsolid. Yield: 71%. Identification was performed by elementary analysisof C, H and N and ¹H-NMR.

[0775]¹H-NMR (CDCl₃, ppm): δ 8.40 (d, J=5.4 Hz, 1H, btp), 8.35 (d, J=5.1Hz, 1H, btp), 7.79 (m, 2H, btp), 7.63 (m, 4H, btp), 7.04 (m, 4H, btp), 56.81 (t, J=7.3 Hz, 2H, btp), 6.20 (t, J=6.8 Hz, 2H, btp), 5.24 (s, 1H,diketonate-methine), 3.89 (dd, J=8.1, 5.1 Hz, 1H, —CHH′—OH), 3.80 (dd,J=8.1, 5.1 Hz, 1H, —CHH′—OH), 2.92 (t, J=5.1 Hz, 1H, OH), 1.83 (s, 3H,diketonate-methyl). Elementary analysis Calcd: C 51.15, H 3.18, N 3.85.(C₃₁H₂₃IrN₂O₃S₃) Found: C 51.41, H 3.36, N 3.49.

[0776]

[0777] (2) As shown in the Reaction Scheme below, Ir(btp)₂(1-OH-acac)was allowed to react with MOI by addition reaction to synthesizeIr(btp)₂(1-MOI-acac).

[0778] That is, 177 mg of Ir(btp)₂(1-OH-acac), 3.0 mg (0.086 mmol) ofBHT and 20 mg (0.032 mmol) of DBTL were dissolved in 10 ml of THF and100 mg (0.64 mmol) of MOI was added thereto. The obtained mixture washeated-under reflux for 2 hours in an oil bath. Then, the reactionmixture cooled to room temperature was dried under reduced pressure andthe residue was purified by silica gel column chromatography (eluent:amixed solvent of hexane/dichloro-methane/acetone of 10:20:3 (by volumeratio)). A main product having a reddish brown color that eluted secondwas separated and concentrated to dryness under reduced pressure. Thesolid was dissolved in a mixed solvent of dichloromethane/hexane andrecrystallized therefrom at −20° C. to obtain 173 mg (0.20 mmol) of theobjective Ir(btp)₂(1-MOI-acac) as reddish brown needle crystal. Yield:81%. Identification was performed by elementary analysis of C, H and Nand ¹H-NMR.

[0779]¹H-NMR (CDCl₃, ppm): δ 8.49 (d, J=5.7 Hz, 1H, btp), 8.40 (d, J=5.4Hz, 1H, btp), 7.74 (m, 2H, btp), 7.61 (m, 4H, btp), 7.03 (m, 4H, btp),6.80 (m, 2H, btp), 6.21 (m, 2H, btp), 6.06 (s, 1H, olefinic), 5.55 (s,1H, olefinic), 5.31 (s, 1H, diketonate-methine), 4.92 (br-s, 1H, NH),4.25 (s, 2H, N—C(═O)—O—CH₂—), 3.97 (m, 2H, N—CH₂—CH₂—O), 3.16 (m, 2H,N—CH₂—CH₂—O), 1.91 (s, 3H, CH₃C(═CH₂)—), 1.81 (s, 3H,diketonate-methyl). Elementary analysis Calcd: C 51.69, H 3.65, N 4.76.(C₃₈H₃₂IrN₃O₆S₂) Found: C 51.88, H 3.65, N 4.51.

[0780]

EXAMPLE 67 Synthesis of N-vinylcarbazole/Ir(btp)₂[-(StMe)-acac]copolymer(hereinafter, abbreviated as VCz-co-Ir(btp)₂[1-(StMe)-acac])

[0781] The titled copolymer was synthesized as a light emitting materialcontaining Ir(btp)₂[1-(StMe)-acac] as a unit having the function ofluminescence and N-vinylcarbazole as a unit having the function of holetransportation.

[0782] 1.55 g (8.0 mmol) of N-vinylcarbazole, 33 mg (0.04 mmol) ofIr(btp)₂[1-(StMe)-acac], and 13 mg (0.08 mmol) of AIBN were dissolved in40 ml of dry toluene and argon was blown into the obtained solution for1 hour. This solution was warmed up to 80° C. to initiate polymerizationreaction and the reaction mixture was stirred as it was for 8 hours.After cooling, the reaction mixture was dripped into 250 ml of methanolto precipitate a polymer, which was recovered by filtration. Further,the recovered polymer was dissolved in 25 ml of chloroform. Thissolution was purified by dripping it into 250 ml of methanol toreprecipitate the polymer and dried in vacuum at 60° C. for 12 hours toobtain 1.11 g of the objective compound VCz-co-Ir(btp)₂[1-(StMe)-acac].Table 7 shows yields, results of GPC measurements, and Ir complexcontents measured by ICP elementary analyses.

EXAMPLES 68 to 70

[0783] Copolymers were synthesized in the same manner as in Example 67except that in place of [1-(StMe)-acac] the polymerizable compoundsprepared in Examples 64 to 66, respectively, were used. Table 7 showsyields, results of GPC measurements, and Ir complex contents measured byICP elementary analyses. TABLE 7 Ir Complex GPC Measurement ContentExample Polymer Recovery (%) Mn Mw Mw/Mn (mol %) 67 VCz-co-Ir(btp)₂[1-71 4500 10800 2.40 0.59 (StMe)acac] 68 VCz-co-Ir(btp)₂[1- 73 4300 107002.52 0.81 (MA-Ph—Me)acac] 69 VCz-co-Ir(btp)₂[1- 58 4300 10900 2.55 0.89(MOI—Ph—Me)acac] 70 VCz-co-Ir(btp)₂(1- 72 4400 11800 2.66 0.61 MOI-acac)

EXAMPLES 71 to 74 Fabrication and Evaluation of Organic Light EmittingElement

[0784] Organic light emitting devices were fabricated in the same manneras in Examples 57 to 62 except that the light emitting materials shownin Table 8 were used and their luminance was measured.

[0785] As a result, the luminescence starting voltage and initialluminance at 20 V as shown in Table 8 were obtained (average of fourdevices for each light emitting material). TABLE 8 20 V LuminescenceInitial Exam- Light Emitting Material Starting Luminance ple PolymerExample voltage (V) (cd/m²) 71 VCz-co-Ir(btp)₂[1- 70 9 420 (StMe)acac]72 VCz-co-Ir(btp)₂[1- 71 9 400 (MA-Ph-Me)acac] 73 VCz-co-Ir(btp)₂[1- 729 360 (MOI-Ph-Me)acac] 74 VCz-co-Ir(btp)₂(1- 73 9 390 MOI-acac)

EXAMPLE 75 Synthesis of a Polymerizable Compoundbis(2-(4-methacryloyloxyphenyl)pyridinato)(acetylacetonato)Iridium (III)(hereinafter abbreviated as Ir(4-MA-PPy)₂(acac))

[0786] (1) As shown in the Reaction Scheme below, a binuclear complex ofiridium, di(μ-chloro)tetrakis (2-(4-hydroxyphenyl)pyridine)diiridium(III) (hereinafter abbreviated as [Ir(4-HO—PPy)₂Cl]₂) was synthesized.

[0787] That is, 0.86 g (5.0 mmol) of 4-HO—PPy prepared in the samemanner as in Example 27(1) and (2) and 1.00 g of sodiumhexachloroiridate (III) hydrate were dissolved in 40 ml of a mixedsolvent of 2-ethoxyethanol:water=3:1 (by volume ratio) and argon gas wasblown into the obtained solution for 30 minutes. Thereafter, thesolution was stirred under reflux for 6 hours. Then, the solvent wasdistilled off and the remaining solid was washed with distilled waterand with chloroform, followed by drying in vacuum for 5 hours to obtain0.63 g of [Ir(4-HO—PPy)₂Cl]₂ as yellow powder. Yield: 74%.Identification was performed by elementary analysis of C, H and N and¹H-NMR.

[0788]¹H-NMR (DMSO-d₆, ppm): δ 9.66(d, 2H, J=5.9 Hz), 9.38(d, 2H, J=5.7Hz), 8.0-7.9(m, 8H), 7.61(d, 2H, J=8.1 Hz), 7.54(d, 2H, J=8.4 Hz),7.38(dd, 2H, J=6.2, 6.2 Hz), 7.26(dd, 2H, J=5.7, 5.7 Hz), 6.33(dd, 2H,J=8.6, 2.4 Hz), 6.28(dd, 2H, J=8.4, 2.4 Hz), 5.67(d, 2H, J=2.2 Hz),5.12(d, 2H, J=2.4 Hz). Elementary analysis Calcd: C 46.52, H 2.84, N4.93. Found: C 46.66, H 2.89, N 4.90.

[0789]

[0790] (2) As shown in the Reaction Scheme below,bis(2-(4-hydroxyphenyl)pyridinato)(acetylacetonato)iridium (III)(hereinafter abbreviated as (Ir(4-HO—PPy)₂(acac)) was synthesized.

[0791] That is, 20 ml of dry N,N-dimethylformamide (hereinafterabbreviated as DMF) and 60.0 mg (0.6 mmol) of 2,4-pentanedione wereadded to 227.2 mg (0.2 mmol) of [Ir(4-HO—PPy)₂Cl]₂ and 212.0 mg (2.0mmol) of sodium carbonate under argon stream and the mixture was stirredat 80° C. for 2 hours. After adding 50 ml of water, the reaction mixturewas extracted with chloroform and washed with saturated saline and withdistilled water. The organic layer was dried over magnesium sulfate andthen concentrated and purified by column chromatography (silica gel,methanol:chloroform=5:95 by volume ratio). Further purification of theproduct by recrystallization from hexane/acetone afforded 152.0mg ofIr(4-HO—PPy)₂(acac) as yellow crystal. Yield: 60%. Identification wasperformed by elementary analysis of C, H and N and ¹H-NMR.

[0792]¹H-NMR (CDCl₃, ppm): δ 8.35(d, 2H, J=5.7 Hz), 7.7-7.6(m, 4 H),7.41(d, 2H, J=10.6 Hz), 7.04(ddd, 2H, J=5.8, 5.8, 2.4 Hz), 6.33(dd, 2H,J=8.4, 2.4 Hz), 5.70(d, 2H, J=2.7 Hz), 5.24(s, 1H), 1.78(s, 6 H).Elementary analysis Calcd: C 51.34, H 3.67, N 4.43. Found: C 51.31, H3.76, N 4.40.

[0793]

[0794] (3) As shown in the Reaction Scheme below, Ir(4-MA-PPy)₂(acac)was synthesized.

[0795] That is, 63.2 mg (0.1 mmol) of Ir(4-HO—PPy)₂(acac) and 0.1 mg of2,6-di-tertbutyl-4-methylphenol (hereinafter abbreviated as BHT) weredissolved in 10 ml of dry THF under argon stream. To the solution wereadded 81.0 mg (0.8 mmol) of triethylamine and 41.8 mg (0.4 mmol) ofmethacryloyl chloride and the mixture was stirred at room temperaturefor 2 hours. 100 ml of water was added to the reaction mixture and thereaction mixture was extracted with chloroform. The extract was washedwith saturated saline and with distilled water. The organic layer wasdried over magnesium sulfate, concentrated and purified by columnchromatography (silica gel, methanol:chloroform=2:98 by volume ratio).Recrystallization of the product from hexane/chloroform afforded 65.3 mgof Ir(4-MA-PPy)₂(acac) as yellow crystal. Yield: 85%. Identification wasperformed by elementary analysis of C, H and N and ¹H-NMR.

[0796]¹H-NMR (DMSO-d₆, ppm): δ 8.38(d, 2H, J=5.7 Hz), 8.15(d, 2H, J=8.6Hz), 7.95(m, 2H), 7.78(d, 2H, J=8.9 Hz), 7.39(m, 2H), 6.61(dd, 2H,J=8.4, 2.4 Hz), 6.09(s, 2H), 5.76(s, 2H), 5.71(d, 2H, J=2.4 Hz), 5.27(s,1H), 1.86(s, 3 H), 1.73(s, 3 H). Elementary analysis Calcd: C 54.75, H4.07, N 3.65. Found: C 54.68, H 4.13, N 3.61.

[0797]

EXAMPLE 76 Synthesis of a Polymerizable Compoundbis(2-(4-(2-methacryloyloxy)ethylcarbamoyloxy)phenyl)pyridinato)(acetylacetonato)Iridium(III) (hereinafter abbreviated as Ir(4-MOI—PPy)₂(acac))

[0798] As shown in the Reaction Scheme below, Ir(4-MOI—PPy)₂(acac) wassynthesized.

[0799] That is, 63.2 mg (0.1 mmol) of Ir(4-HO—PPy)₂(acac), theintermediate in Example 75, 0.2 mg of BHT and 1.3 mg of dibutyltin (IV)dilaurate (hereinafter abbreviated as DBTL) were dissolved in 10 ml ofdry THF under argon stream. To this solution was further added 62.0 mg(0.4 mmol) of 2-methacryloyloxyethyl isocyanate (Trade name “KarenzMOI”, manufactured by Showa Denko K. K., hereinafter sometimes referredto as “MOI”) and the mixture was stirred at 50° C. for 1 hour. To thereaction mixture was added 50 ml of water and then the reaction mixturewas extracted with chloroform. The extract was washed with saturatedsaline and with distilled water. After drying the organic layer overmagnesium sulfate, it was concentrated and purified by columnchromatography (silica gel, methanol:chloroform=5:95 (by volume ratio)).Recrystallization of the purified product from hexane/chloroformafforded 73.5 mg of Ir(4-MOI—PPy)₂(acac) as yellow crystal. Yield: 78%.Identification was performed by ¹H-NMR and elementary analysis of C, Hand N.

[0800]¹H-NMR (DMSO-d₆, ppm): δ 8.37 (d, 2H, J=5. 9 Hz), 8.1 (d, 2H,J=7.8 Hz), 7.93(dd, 2H, J=8.0, 8.0 Hz), 7.70(d, 2H, J=8.6 Hz), 7.64(t,2H), 7.4(dd, 2H, J=6.3, 6.3 Hz), 6.56(dd, 2H, J=8.2, 2.3 Hz), 6.02(s,2H), 5.7-5.6(m, 4H), 5.26(s, 1H), 4.06(t, 4H, J=5.4 Hz), 3.3(m, 4H,overlapped with H₂O), 1.85(s, 6H), 1.73(s, 6H). Elementary analysisCalcd: C 52.28, H 4.39, N 5.95. Found: C 52.22, H 4.47, N 5.86.

[0801]

EXAMPLE 77 Synthesis of a Polymerizable Compoundbis(2-(4-(4-vinylbenzyloxy)phenyl)pyridinato)(acetylacetonato)Iridium(III) (hereinafter abbreviated as Ir(4-ST-PPy)₂(acac)).

[0802] As shown in the Reaction Scheme below, Ir(4-ST-PPy)₂(acac) wassynthesized.

[0803] That is, 63.2 mg (0.1 mmol) of Ir(4-HO—PPy)₂(acac), theintermediate in Example 75, 0.2 mg of BHT and 138.2 mg (1.0 mmol) ofpotassium carbonate were dissolved in 10 ml dry DMF under argon stream.To this solution was added 61.0 mg (0.4 mmol) of 4-vinylbenzyl chloride,and the mixture was stirred at 80° C. for 6 hours. To the reactionmixture was added 50 ml of water and the reaction mixture was extractedwith chloroform. The extract was washed with saturated saline and withdistilled water. After drying the organic layer over magnesium sulfate,it was concentrated and purified by column chromatography (silica gel,methanol: chloroform=5:95 (by volume ratio)). Recrystallization of thepurified product from hexane/chloroform afforded 62.2 mg ofIr(4-ST-PPy)₂(acac) as yellow crystal. Yield: 72%. Identification wasperformed by ¹H-NMR and elementary analysis of C, H and N.

[0804]¹H-NMR (DMSO-d₆, ppm):5 8.37(d, 2H, J=5.9 Hz), 8.13(d, 2H, J=8.4Hz), 8.0-7.9(m, 2H), 7.75(d, 2H, J=8.9 Hz), 7.5-7.3(m, 10 H), 6.73(m,2H), 6.59(dd, 2H, J=8.2, 2.4 Hz), 5.88(d, 2H, J=17.8 Hz), 5.73(d, 2H,J=2.4 Hz), 5.3-5.2(m, 7 H), 1.78(s, 3 H). Elementary analysis Calcd: C62.55, H 4.55, N 3.24. Found: C 62.58, H 4.65, N 3.20.

[0805]

EXAMPLE 78 Second Method for the Synthesis of a Polymerizable CompoundIr(4-MA-PPy)₂(acac)

[0806] (1) As 'shown in the Reaction Scheme below,2-(4-methacryloyloxyphenyl)pyridine (hereinafter abbreviated as4-MA-PPy) was synthesized.

[0807] That is, 3.42 g (20.0 mmol) of 4-HO—PPy, the intermediate inExample 75 was dissolved in 20 ml of dry dichloromethane under argonstream. To this solution was added 6.07 g (60.0 mmol) of triethylamineand 3.14 g (30.0 mmol) of methacryloyl chloride was dripped to themixture over 1 hour and then the resultant mixture was stirred at roomtemperature for 2 hours. To the reaction mixture was added 100 ml ofwater and the mixture the reaction mixture was extracted withchloroform. The extract was washed with saturated saline and with water.After drying the organic layer over magnesium sulfate, it wasconcentrated and purified by column chromatography (silica gel,chloroform). Recrystallization of the purified product fromhexane/chloroform afforded 4.16 g of 4-MA-PPy as colorless crystal.Yield: 87%. Identification was performed by ¹H-NMR and elementaryanalysis of C, H and N.

[0808]¹H-7NMR (CDCl₃, ppm): δ 8.63(d, 1H, J=4.9 Hz), 7.98(d, 2H, J=8.6Hz), 7.5-7.6(m, 2H), 7.2-7.1(m, 3H), 6.01(s, 1H), 5.53(s 1H), 1.83(s,3H). Elementary analysis Calcd: C 75.30, H 5.48, N 5.85. Found: C 75.26,H 5.53, N 5.79.

[0809]

[0810] (2) As shown in the Reaction Scheme below, a binuclear complex ofiridium, di(μ-chloro)tetrakis(2-(4-methacryloyloxy-phenyl)pyridine)diiridium (III) (hereinafterabbreviated as [Ir(4-MA-PPy)₂Cl]₂) was synthesized.

[0811] That is, 1.20 g (5.0 mmol) of 4-MA-PPy and 1.00 g of sodiumhexachloroiridate (III) hydrate were dissolved in 40 ml of a mixedsolvent of 2-ethoxyethanol:water=3:1 (by volume ratio) and argon gas wasblown into the obtained solution for 30 minutes. Thereafter, thesolution was stirred under reflux for 6 hours. The precipitate formedwas collected by filtration and washed with ethanol and with a smallamount of acetone, followed by drying in vacuum for 5 hours to obtain0.87 g of [Ir(4-MA-PPy)₂Cl]₂ as yellow powder. Yield: 82%.Identification was performed by ¹H-NMR and elementary analysis of C, Hand N.

[0812]¹H-NMR (DMSO-d₆, ppm): δ 9.64(d, 2H, J=5.7 Hz), 9.37(d, 2H, J=5.7Hz), 8.2-8.1(m, 4 H), 7.75(m, 4 H), 7.6-7.5(m, 8 H), 6.56(m, 4 H),5.87(d, 2H, J=2.4 Hz), 5.38(d, 2H, J=2.4 Hz), 6.09(s, 2H), 6.03(s, 2H),5.79(s, 2H), 5.74(s, 2H), 1.89(s, 6H), 1.87(s, 6H). Elementary analysisCalcd: C 51.17, H 3.44, N 3.98. Found: C 51.13, H 3.51, N 3.97.

[0813]

[0814] (3) As shown in the Reaction Scheme below, Ir(4-MA-PPy)₂(acac)was synthesized.

[0815] That is, 20 ml of dry DMF and 60.0 mg (0.6 mmol) of2,4-pentanedione were added to 281.7 mg (0.2 mmol) of [Ir(4-MA-PPy)₂Cl]₂and 212.0 mg (2.0 mmol) of sodium carbonate. The mixture was stirred at80° C. for 2 hours. After adding 100 ml of water to the reactionmixture, the reaction mixture was extracted with chloroform and theextract was washed with saturated saline and with distilled water. Afterdrying the organic layer over magnesium sulfate, it was concentrated andpurified by column chromatography (silica gel, methanol:chloroform=2:98(by volume ratio)). Recrystallization of the purified product fromhexane/chloroform afforded 221.1 mg of Ir(4-MA-PPy)₂(acac) as yellowcrystal. Yield: 72%. Identification was performed by ¹H-NMR andelementary analysis of C, H and N, which verified that this wasidentical with the compound synthesized in Example 75.

EXAMPLE 79 Synthesis of N-vinylcarbazole/Ir(4-MA-PPy)₂(acac) Copolymer(Hereinafter, Abbreviated as VCz-co-Ir(4-MA-PPY)₂(acac))

[0816] The titled copolymer was synthesized as a light emitting materialcontaining Ir(4-MA-PPy)₂(acac) as a unit having the function ofluminescence and N-vinylcarbazole as a unit having the function of holetransportation.

[0817] 966 mg (5.0 mmol) of N-vinylcarbazole, 38.4 mg (0.05 mmol) ofIr(4-MA-PPy)₂(acac), and 8.2 mg (0.05 mmol) of AIBN were dissolved in 25ml of dry toluene and argon was blown into the obtained solution for 1hour. This solution was warmed up to 80° C. to initiate polymerizationreaction and the reaction mixture was stirred as it was for 8 hours.After cooling, the reaction mixture was dripped into 250 ml of methanolto precipitate a polymer, which was recovered by filtration. Further,the recovered polymer was dissolved in 25 ml of chloroform. Thissolution was purified by dripping it into 250 ml of methanol toreprecipitate the polymer and dried in vacuum at 60° C. for 12 hours toobtain 755 mg of the objective compound VCz-co-Ir(4-MA-PPy)₂(acac).Table 9 shows yields, results of GPC measurements, and Ir complexcontents measured by ICP elementary analyses. Ir(4-MA-PPy)₂(acac), whichwas a bifunctional monomer, had a low degree of crosslinking so thatproduced no insoluble matter since its amount was very small as comparedwith the amount of N-vinylcarbazole.

EXAMPLES 80 to 81

[0818] Copolymers were synthesized in the same manner as in Example 79except that in place of Ir(4-MA-PPy)₂(acac), equivalent moles of thepolymerizable compounds prepared in Examples 76 to 77, respectively,were used. Table 9 shows yields, results of GPC measurements, and Ircomplex contents measured by ICP elementary analyses. TABLE 9 Ir ComplexGPC Measurement Content Example Polymer Recovery (%) Mn Mw Mw/Mn (mol %)79 VCz-co-Ir(4-MA- 75 7100 29100 4.10 1.09 PPy)₂(acac) 80 VCz-co-Ir(4-72 6500 28300 4.35 1.07 MOI—PPy)₂(acac) 81 VCz-co-Ir(4-ST- 77 6600 306004.64 1.06 PPy)₂(acac)

EXAMPLES 82 to 84 Fabrication and Evaluation of Organic Light EmittingElement

[0819] Organic light emitting devices were fabricated in the same manneras in Examples 57 to 62 except that the light emitting materials shownin Table 10 were used and their luminance was measured.

[0820] As a result, the luminescence starting voltage, initial luminanceat 15 V, and luminance after 240 hours' continuous luminescence at afixed voltage of 15 V as shown in Table 10 were obtained (as averagevalues of four devices for each light emitting material).

COMPARATIVE EXAMPLE 4

[0821] Organic light emitting devices were fabricated in the same manneras in Examples 82 to 84 except that a coating solution was prepared bydissolving containing 19.5 mg of poly(N-vinylcarbazole) (manufactured byTokyo Kasei Kogyo Co., Ltd.) as a hole transporting material, 1.5 mg ofa compound of the formula

[0822] synthesized by the known method (S. Lamansky, et al., InorganicChemistry, 40, 1704 (2001)) as a light emitting material, and 9.0 mg of2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD)(manufactured by Tokyo Kasei Kogyo Co., Ltd.) were dissolved in 2970 mgof chloroform (manufactured by Wako Pure Chemical Industries, Ltd.) andthe obtained solution was filtered through a filter having a pore sizeof 0. 2 μm, and luminance of the devices was measured. As a result, theluminescence starting voltage, initial luminance at 15 V, and luminanceafter 200 hours' continuous luminescence at a fixed voltage of 15 V asshown in Table 10 were obtained (as average values of four devices foreach light emitting material). TABLE 10 15 V Limunance Luminescence(cd/m²) Starting After Example Voltage (V) Initial 200 Hours 85 7 370330 86 7 330 290 87 7 410 350 Comparative 7 360 120 Example 4

[0823] Industrial Applicability

[0824] By using the polymer light emitting material of the presentinvention, energy in an excited triplet state can be efficientlyconverted to light emission or luminescence so that an organic lightemitting device exhibiting high luminance and high durability can beprovided.

[0825] Furthermore, by using non-crosslinking and/or crosslinkingpolymer light emitting material obtained by forming the polymerizablelight emitting compound into a film, an organic light emitting devicehaving good processability can be provided.

[0826] The polymerizable compounds of the formulae (C-1), (D-1), (E-1),(F-1) or (G-1) give rise to novel polymers containing an iridium complexpart. By using such polymers as a light emitting materials for organiclight emitting devices, organic light emitting devices that efficientlyemit from an excited triplet state, are excellent in stability, can bedesigned so as to have a large area and hence are suitable for massproduction can be provided.

1. A polymer light emitting material, wherein the material has a lightemitting mechanism based on transition from an excited triplet state toa ground state or transition through an excited triplet state to aground state of an electron energy level, and the material comprises anonionic light emitting part which constitutes a part of the polymer oris bound to the polymer.
 2. The polymer light emitting materialaccording to claim 1, wherein the light emitting part is formed bybinding a metal atom to at least one site of the polymer.
 3. The polymerlight emitting material according to claim 2, wherein the metal atom isbound by one or more covalent bonds and/or one or more coordinate bonds.4. The polymer light emitting material according to claim 1, wherein thelight emitting part is a metal complex structure having a metal atom oran organometallic structure having a metal atom.
 5. The polymer lightemitting material according to claim 2 or 4, wherein the metal atom is atransition metal atom.
 6. The polymer light emitting material accordingto claim 5, wherein the transition metal atom is a transition metal atombelonging to the sixth period of the periodic table.
 7. The polymerlight emitting material according to claim 6, wherein the transitionmetal atom is iridium.
 8. The polymer light emitting material accordingto claim 6, wherein the transition metal is platinum.
 9. The polymerlight emitting material according to claim 2 or 4, wherein the metalatom is a rare earth metal atom.
 10. The polymer light emitting materialaccording to any one of claims 1 to 9, wherein the light emitting partis formed by binding containing a coordinate bond formed by a metal atomand a nitrogen atom of the polymer.
 11. The polymer light emittingmaterial according to claim 10, wherein the nitrogen atom of the polymeris a nitrogen atom of a pyridine skeleton and/or pyrimidine skeletonand/or quinoline skeleton on the side of the polymer.
 12. The polymerlight emitting material according to claim 10, wherein the nitrogen atomof the polymer is a nitrogen atom of a phenylpyridine skeleton on theside of the polymer.
 13. The polymer light emitting material accordingto claim 10, wherein the nitrogen atom of the polymer is a nitrogen atomof a benzothienyl-pyridine skeleton on the side of the polymer.
 14. Thepolymer light emitting material according to claim 1, comprising a lightemitting part that contains a phosphorescent moiety and a fluorescentmoiety with fluorescence occurring from the fluorescent moiety throughan excited triplet state of the phosphorescent moiety and an excitedtriplet state of the fluorescent moiety, wherein at least one of thephosphorescent moiety and the fluorescent moiety constitutes a part ofthe polymer or is bound to the polymer.
 15. The polymer light emittingmaterial according to claim 1, wherein the material is obtained bypolymerizing a polymerizable composition containing at least one lightemitting compound.
 16. The polymer light emitting material according toclaim 15, wherein the light emitting compound is a polymerizable lightemitting compound.
 17. The polymer light emitting material according toclaim 15, wherein the polymer obtained by polymerizing the compositionhas no crosslinking structure.
 18. The polymer light emitting materialaccording to claim 16, wherein the at least one polymerizable lightemitting compound is a crosslinking polymerizable light emittingcompound having two or more polymerizable functional groups and thepolymer after the polymerization is a crosslinked polymer.
 19. Thepolymer light emitting material according to any one of claims 15 to 18,wherein the polymerizable composition contains at least onepolymerizable compound other than the light emitting compound.
 20. Thepolymer light emitting material according to claim 19, wherein the atleast one polymerizable compound other than the light emitting compoundis a polymerizable electron transporting compound.
 21. The polymer lightemitting material according to claim 19, wherein at least onepolymerizable compound other than the light emitting compound is acrosslinking polymerizable compound having two or more polymerizablefunctional groups.
 22. The polymer light emitting material according toclaim 15, wherein a light emitting part of the polymer light emittingmaterial is a metal complex structure having a metal atom or anorganometallic structure having a metal atom.
 23. The polymer lightemitting material according to claim 22, wherein the metal atom is atransition metal atom.
 24. The polymer light emitting material accordingto claim 22, wherein the metal atom is a rare earth metal atom.
 25. Thepolymer light emitting material according to any one of claims 22 to 24,wherein the light emitting part contains a nitrogen atom in a complexstructure forming part or in an organometallic structure forming part.26. The polymer light emitting material according to claim 25, whereinthe light emitting part has a pyridine skeleton, a pyrimidine skeletonand/or a quinoline skeleton in a complex structure forming part or in anorganometallic structure forming part.
 27. The polymer light emittingmaterial according to claim 16, wherein the polymerizable light emittingcompound is a polymerizable compound represented by the formula (C-1)below:

wherein at least one of A^(C), B^(C), and C^(C) represents a substituenthaving a polymerizable functional group, and the remainder of A^(C),B^(C), and C^(C) independently represent a hydrogen atom, a halogenatom, a nitro group, an amino group, a sulfonic acid group, a sulfonicacid ester group, or an organic group having 1 to 20 carbon atoms whichmay have one or more heteroatoms; and R¹ to R²¹ independently representa hydrogen atom, a halogen atom, a nitro group, an amino group, asulfonic acid group, a sulfonic acid ester group, or an organic grouphaving 1 to 20 carbon atoms which may have one or more heteroatoms. 28.The polymer light emitting material according to claim 16, wherein thepolymerizable light emitting compound is a polymerizable compoundrepresented by the formula (D-1) below:

wherein at least one of X^(1D), y^(1D), and Z^(1D) represents asubstituent having a polymerizable functional group, and the remainderof X^(1D), Y^(1D), and Z^(1D) independently represent a hydrogen atom,or an organic group having 1 to 20 carbon atoms which may have one ormore heteroatoms; and R¹ to R¹⁶ independently represent a hydrogen atom,a halogen atom, a nitro group, an amino group, a sulfonic acid group, asulfonic acid ester group, or an organic group having 1 to 20 carbonatoms which may have one or more heteroatoms.
 29. The polymer lightemitting material according to claim 16, wherein the polymerizable lightemitting compound is a polymerizable compound represented by the formula(E-1) below:

wherein X^(E) represents a substituent having a polymerizable functionalgroup; R^(1E), R^(2E) and R^(3E) independently represents a hydrogenatom, a halogen atom, or an organic group having 1 to 20 carbon atoms;and R⁴ to R¹⁹ independently represent a hydrogen atom, a halogen atom, anitro group, an amino group, a sulfonic acid group, a sulfonic acidester group, or an organic group having 1 to 20 carbon atoms which mayhave one or more heteroatoms.
 30. The polymer light emitting materialaccording to claim 16, wherein the polymerizable light emitting compoundis a polymerizable compound represented by the formula (F-1) below:

wherein at least one of X^(1F), Y^(1F), and Z^(1F) represents asubstituent having a polymerizable functional group, and the remainderof X^(1F), Y^(1F), and Z^(1F) independently represent a hydrogen atom, ahalogen atom, or an organic group having 1 to 20 carbon atoms which mayhave one or more heteroatoms; and R¹ to R¹⁶ independently represent ahydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonicacid group, a sulfonic acid ester group, or an organic group having 1 to20 carbon atoms which may have one or more heteroatoms.
 31. The polymerlight emitting material according to claim 16, wherein the polymerizablelight emitting compound is a polymerizable compound represented by theformula (G-1) below:

wherein L represents a monovalent anionic bidentate ligand; X^(G)represents a substituent having a polymerizable functional group; and R¹to R⁷ independently represent a hydrogen atom, a halogen atom, a nitrogroup, an amino group, a sulfonic acid group, a sulfonic acid estergroup, or an organic group having 1 to 20 carbon atoms which may haveone or more heteroatoms.
 32. A light emitting composition comprising thepolymer light emitting material according to any one of claims 1 to 31,and a carrier transporting polymer compound.
 33. The light emittingcomposition according to claim 32, wherein the carrier transportingpolymer compound is a hole transporting polymer compound.
 34. The lightemitting composition according to claim 32, wherein the carriertransporting polymer compound is an electron transporting polymercompound.
 35. A light emitting composition comprising the light emittingmaterial according to any one of claims 1 to 31, and a carriertransporting low molecular weight compound.
 36. The light emittingcomposition according to claim 35, wherein the carrier transporting lowmolecular weight compound is a hole transporting low molecular weightcompound.
 37. The light emitting composition according to claim 35,wherein the carrier transporting low molecular weight compound is anelectron transporting low molecular weight compound.
 38. A layercontaining a light emitting material for organic light emitting device,wherein a light emitting material is a polymer light emitting materialdescribed in claim
 1. 39. The layer containing a light emitting materialfor organic light emitting device according to claim 38, obtained byforming into a film a polymer light emitting material described inclaim
 1. 40. The layer containing a light emitting material for organiclight emitting device according to claim 39, wherein the polymer lightemitting material has no crosslinking structure.
 41. The layercontaining a light emitting material for organic light emitting deviceaccording to claim 38, wherein the polymer light emitting material isobtained by forming a polymerizable composition containing at least onelight emitting compound into a film and then polymerizing it.
 42. Thelayer containing a light emitting material for organic light emittingdevice according to claim 41, wherein the polymer light emittingmaterial has no crosslinking structure.
 43. The layer containing a lightemitting material for organic light emitting device according to claim41, wherein the polymer light emitting material has a crosslinkingstructure.
 44. An organic light emitting device comprising the polymerlight emitting material according to any one of claims 1 to
 31. 45. Theorganic light emitting device according to claim 44, comprising a lightemitting layer comprising the polymer light emitting material describedin any one of claims 1 to 31 having both sides or one side thereof anelectron transporting layer of a coated type, and/or a hole transportinglayer of a coated type.